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Materials Characterisation V

Computational Methods
and Experiments

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FIFTH INTERNATIONAL CONFERENCE ON


COMPUTATIONAL METHODS AND EXPERIMENTS IN
MATERIALS CHARACTERISATION
MATERIALS CHARACTERISATION 2011

CONFERENCE CHAIRMEN
A.A. Mammoli
University of New Mexico, USA
C.A. Brebbia
Wessex Institute of Technology, UK
A. Klemm
Glasgow Caledonian University, UK

INTERNATIONAL SCIENTIFIC ADVISORY COMMITTEE


G. Badalians Gholikandi
A. Bayton
A. Galybin
H. Huh
G. Moriconi
P. Prochazka
I. Sanchez
P. Viot

Organised by
Wessex Institute of Technology, UK
University of New Mexico, USA
Sponsored by
WIT Transactions on Engineering Sciences

WIT Transactions
Transactions Editor
Carlos Brebbia
Wessex Institute of Technology
Ashurst Lodge, Ashurst
Southampton SO40 7AA, UK
Email: carlos@wessex.ac.uk

Editorial Board
B Abersek University of Maribor, Slovenia
Y N Abousleiman University of Oklahoma,

G Belingardi Politecnico di Torino, Italy


R Belmans Katholieke Universiteit Leuven,

P L Aguilar University of Extremadura, Spain


K S Al Jabri Sultan Qaboos University, Oman
E Alarcon Universidad Politecnica de Madrid,

C D Bertram The University of New South

USA

Spain

A Aldama IMTA, Mexico


C Alessandri Universita di Ferrara, Italy
D Almorza Gomar University of Cadiz,
Spain

B Alzahabi Kettering University, USA


J A C Ambrosio IDMEC, Portugal
A M Amer Cairo University, Egypt
S A Anagnostopoulos University of Patras,
Greece

M Andretta Montecatini, Italy


E Angelino A.R.P.A. Lombardia, Italy
H Antes Technische Universitat Braunschweig,
Germany

M A Atherton South Bank University, UK


A G Atkins University of Reading, UK
D Aubry Ecole Centrale de Paris, France
H Azegami Toyohashi University of
Technology, Japan

A F M Azevedo University of Porto, Portugal


J Baish Bucknell University, USA
J M Baldasano Universitat Politecnica de
Catalunya, Spain
J G Bartzis Institute of Nuclear Technology,
Greece
A Bejan Duke University, USA
M P Bekakos Democritus University of
Thrace, Greece

Belgium

Wales, Australia

D E Beskos University of Patras, Greece


S K Bhattacharyya Indian Institute of
Technology, India

E Blums Latvian Academy of Sciences, Latvia


J Boarder Cartref Consulting Systems, UK
B Bobee Institut National de la Recherche
Scientifique, Canada

H Boileau ESIGEC, France


J J Bommer Imperial College London, UK
M Bonnet Ecole Polytechnique, France
C A Borrego University of Aveiro, Portugal
A R Bretones University of Granada, Spain
J A Bryant University of Exeter, UK
F-G Buchholz Universitat Gesanthochschule
Paderborn, Germany

M B Bush The University of Western


Australia, Australia

F Butera Politecnico di Milano, Italy


J Byrne University of Portsmouth, UK
W Cantwell Liverpool University, UK
D J Cartwright Bucknell University, USA
P G Carydis National Technical University of
Athens, Greece

J J Casares Long Universidad de Santiago de


Compostela, Spain

M A Celia Princeton University, USA


A Chakrabarti Indian Institute of Science,
India

A H-D Cheng University of Mississippi, USA

J Chilton University of Lincoln, UK


C-L Chiu University of Pittsburgh, USA
H Choi Kangnung National University, Korea
A Cieslak Technical University of Lodz,
Poland

S Clement Transport System Centre, Australia


M W Collins Brunel University, UK
J J Connor Massachusetts Institute of
Technology, USA

M C Constantinou State University of New


York at Buffalo, USA

D E Cormack University of Toronto, Canada


M Costantino Royal Bank of Scotland, UK
D F Cutler Royal Botanic Gardens, UK
W Czyczula Krakow University of
Technology, Poland

M da Conceicao Cunha University of


Coimbra, Portugal

L Dvid Kroly Rbert College, Hungary


A Davies University of Hertfordshire, UK
M Davis Temple University, USA
A B de Almeida Instituto Superior Tecnico,
Portugal

E R de Arantes e Oliveira Instituto Superior


Tecnico, Portugal
L De Biase University of Milan, Italy
R de Borst Delft University of Technology,
Netherlands
G De Mey University of Ghent, Belgium
A De Montis Universita di Cagliari, Italy
A De Naeyer Universiteit Ghent, Belgium
W P De Wilde Vrije Universiteit Brussel,
Belgium
L Debnath University of Texas-Pan American,
USA
N J Dedios Mimbela Universidad de
Cordoba, Spain
G Degrande Katholieke Universiteit Leuven,
Belgium
S del Giudice University of Udine, Italy
G Deplano Universita di Cagliari, Italy
I Doltsinis University of Stuttgart, Germany
M Domaszewski Universite de Technologie
de Belfort-Montbeliard, France
J Dominguez University of Seville, Spain
K Dorow Pacific Northwest National
Laboratory, USA
W Dover University College London, UK
C Dowlen South Bank University, UK

J P du Plessis University of Stellenbosch,


South Africa

R Duffell University of Hertfordshire, UK


A Ebel University of Cologne, Germany
E E Edoutos Democritus University of
Thrace, Greece

G K Egan Monash University, Australia


K M Elawadly Alexandria University, Egypt
K-H Elmer Universitat Hannover, Germany
D Elms University of Canterbury, New Zealand
M E M El-Sayed Kettering University, USA
D M Elsom Oxford Brookes University, UK
F Erdogan Lehigh University, USA
F P Escrig University of Seville, Spain
D J Evans Nottingham Trent University, UK
J W Everett Rowan University, USA
M Faghri University of Rhode Island, USA
R A Falconer Cardiff University, UK
M N Fardis University of Patras, Greece
P Fedelinski Silesian Technical University,
Poland

H J S Fernando Arizona State University,


USA

S Finger Carnegie Mellon University, USA


J I Frankel University of Tennessee, USA
D M Fraser University of Cape Town, South
Africa

M J Fritzler University of Calgary, Canada


U Gabbert Otto-von-Guericke Universitat
Magdeburg, Germany

G Gambolati Universita di Padova, Italy


C J Gantes National Technical University of
Athens, Greece

L Gaul Universitat Stuttgart, Germany


A Genco University of Palermo, Italy
N Georgantzis Universitat Jaume I, Spain
P Giudici Universita di Pavia, Italy
F Gomez Universidad Politecnica de Valencia,
Spain

R Gomez Martin University of Granada,


Spain

D Goulias University of Maryland, USA


K G Goulias Pennsylvania State University,
USA

F Grandori Politecnico di Milano, Italy


W E Grant Texas A & M University,
USA

S Grilli University of Rhode Island, USA

R H J Grimshaw Loughborough University,


D Gross Technische Hochschule Darmstadt,

M Karlsson Linkoping University, Sweden


T Katayama Doshisha University, Japan
K L Katsifarakis Aristotle University of

R Grundmann Technische Universitat

J T Katsikadelis National Technical

A Gualtierotti IDHEAP, Switzerland


R C Gupta National University of Singapore,

E Kausel Massachusetts Institute of

UK

Germany

Dresden, Germany

Singapore
J M Hale University of Newcastle, UK
K Hameyer Katholieke Universiteit Leuven,
Belgium
C Hanke Danish Technical University,
Denmark
K Hayami University of Toyko, Japan
Y Hayashi Nagoya University, Japan
L Haydock Newage International Limited, UK
A H Hendrickx Free University of Brussels,
Belgium
C Herman John Hopkins University, USA
S Heslop University of Bristol, UK
I Hideaki Nagoya University, Japan
D A Hills University of Oxford, UK
W F Huebner Southwest Research Institute,
USA
J A C Humphrey Bucknell University, USA
M Y Hussaini Florida State University, USA
W Hutchinson Edith Cowan University,
Australia
T H Hyde University of Nottingham, UK
M Iguchi Science University of Tokyo, Japan
D B Ingham University of Leeds, UK
L Int Panis VITO Expertisecentrum IMS,
Belgium
N Ishikawa National Defence Academy, Japan
J Jaafar UiTm, Malaysia
W Jager Technical University of Dresden,
Germany
Y Jaluria Rutgers University, USA
C M Jefferson University of the West of
England, UK
P R Johnston Griffith University, Australia
D R H Jones University of Cambridge, UK
N Jones University of Liverpool, UK
D Kaliampakos National Technical
University of Athens, Greece
N Kamiya Nagoya University, Japan
D L Karabalis University of Patras, Greece

Thessaloniki, Greece

University of Athens, Greece

Technology, USA

H Kawashima The University of Tokyo,


Japan

B A Kazimee Washington State University,


USA

S Kim University of Wisconsin-Madison, USA


D Kirkland Nicholas Grimshaw & Partners
Ltd, UK

E Kita Nagoya University, Japan


A S Kobayashi University of Washington,
USA

T Kobayashi University of Tokyo, Japan


D Koga Saga University, Japan
S Kotake University of Tokyo, Japan
A N Kounadis National Technical University
of Athens, Greece

W B Kratzig Ruhr Universitat Bochum,


Germany

T Krauthammer Penn State University, USA


C-H Lai University of Greenwich, UK
M Langseth Norwegian University of Science
and Technology, Norway

B S Larsen Technical University of Denmark,


Denmark

F Lattarulo Politecnico di Bari, Italy


A Lebedev Moscow State University, Russia
L J Leon University of Montreal, Canada
D Lewis Mississippi State University, USA
S lghobashi University of California Irvine,
USA

K-C Lin University of New Brunswick,


Canada

A A Liolios Democritus University of Thrace,


Greece

S Lomov Katholieke Universiteit Leuven,


Belgium

J W S Longhurst University of the West of


England, UK

G Loo The University of Auckland, New


Zealand

J Lourenco Universidade do Minho, Portugal


J E Luco University of California at San
Diego, USA

H Lui State Seismological Bureau Harbin,


China

C J Lumsden University of Toronto, Canada


L Lundqvist Division of Transport and

Location Analysis, Sweden


T Lyons Murdoch University, Australia
Y-W Mai University of Sydney, Australia
M Majowiecki University of Bologna, Italy
D Malerba Universit degli Studi di Bari, Italy
G Manara University of Pisa, Italy
B N Mandal Indian Statistical Institute, India
Mander University of Tartu, Estonia
H A Mang Technische Universitat Wien,
Austria
G D Manolis Aristotle University of
Thessaloniki, Greece
W J Mansur COPPE/UFRJ, Brazil
N Marchettini University of Siena, Italy
J D M Marsh Griffith University, Australia
J F Martin-Duque Universidad Complutense,
Spain
T Matsui Nagoya University, Japan
G Mattrisch DaimlerChrysler AG, Germany
F M Mazzolani University of Naples
Federico II, Italy
K McManis University of New Orleans, USA
A C Mendes Universidade de Beira Interior,
Portugal
R A Meric Research Institute for Basic
Sciences, Turkey
J Mikielewicz Polish Academy of Sciences,
Poland
N Milic-Frayling Microsoft Research Ltd,
UK
R A W Mines University of Liverpool, UK
C A Mitchell University of Sydney, Australia
K Miura Kajima Corporation, Japan
A Miyamoto Yamaguchi University, Japan
T Miyoshi Kobe University, Japan
G Molinari University of Genoa, Italy
T B Moodie University of Alberta, Canada
D B Murray Trinity College Dublin, Ireland
G Nakhaeizadeh DaimlerChrysler AG,
Germany
M B Neace Mercer University, USA
D Necsulescu University of Ottawa, Canada
F Neumann University of Vienna, Austria
S-I Nishida Saga University, Japan

H Nisitani Kyushu Sangyo University, Japan


B Notaros University of Massachusetts, USA
P ODonoghue University College Dublin,
Ireland

R O ONeill Oak Ridge National Laboratory,


USA

M Ohkusu Kyushu University, Japan


G Oliveto Universit di Catania, Italy
R Olsen Camp Dresser & McKee Inc., USA
E Oate Universitat Politecnica de Catalunya,
Spain

K Onishi Ibaraki University, Japan


P H Oosthuizen Queens University, Canada
E L Ortiz Imperial College London, UK
E Outa Waseda University, Japan
A S Papageorgiou Rensselaer Polytechnic
Institute, USA

J Park Seoul National University, Korea


G Passerini Universita delle Marche, Italy
B C Patten University of Georgia, USA
G Pelosi University of Florence, Italy
G G Penelis Aristotle University of
Thessaloniki, Greece

W Perrie Bedford Institute of Oceanography,


Canada

R Pietrabissa Politecnico di Milano, Italy


H Pina Instituto Superior Tecnico, Portugal
M F Platzer Naval Postgraduate School, USA
D Poljak University of Split, Croatia
V Popov Wessex Institute of Technology, UK
H Power University of Nottingham, UK
D Prandle Proudman Oceanographic
Laboratory, UK

M Predeleanu University Paris VI, France


M R I Purvis University of Portsmouth, UK
I S Putra Institute of Technology Bandung,
Indonesia

Y A Pykh Russian Academy of Sciences,


Russia

F Rachidi EMC Group, Switzerland


M Rahman Dalhousie University, Canada
K R Rajagopal Texas A & M University, USA
T Rang Tallinn Technical University, Estonia
J Rao Case Western Reserve University, USA
A M Reinhorn State University of New York
at Buffalo, USA

A D Rey McGill University, Canada

D N Riahi University of Illinois at Urbana-

Champaign, USA
B Ribas Spanish National Centre for
Environmental Health, Spain
K Richter Graz University of Technology,
Austria
S Rinaldi Politecnico di Milano, Italy
F Robuste Universitat Politecnica de
Catalunya, Spain
J Roddick Flinders University, Australia
A C Rodrigues Universidade Nova de Lisboa,
Portugal
F Rodrigues Poly Institute of Porto, Portugal
C W Roeder University of Washington, USA
J M Roesset Texas A & M University, USA
W Roetzel Universitaet der Bundeswehr
Hamburg, Germany
V Roje University of Split, Croatia
R Rosset Laboratoire dAerologie, France
J L Rubio Centro de Investigaciones sobre
Desertificacion, Spain
T J Rudolphi Iowa State University, USA
S Russenchuck Magnet Group, Switzerland
H Ryssel Fraunhofer Institut Integrierte
Schaltungen, Germany
S G Saad American University in Cairo, Egypt
M Saiidi University of Nevada-Reno, USA
R San Jose Technical University of Madrid,
Spain
F J Sanchez-Sesma Instituto Mexicano del
Petroleo, Mexico
B Sarler Nova Gorica Polytechnic, Slovenia
S A Savidis Technische Universitat Berlin,
Germany
A Savini Universita de Pavia, Italy
G Schmid Ruhr-Universitat Bochum, Germany
R Schmidt RWTH Aachen, Germany
B Scholtes Universitaet of Kassel, Germany
W Schreiber University of Alabama, USA
A P S Selvadurai McGill University, Canada
J J Sendra University of Seville, Spain
J J Sharp Memorial University of
Newfoundland, Canada
Q Shen Massachusetts Institute of Technology,
USA
X Shixiong Fudan University, China
G C Sih Lehigh University, USA
L C Simoes University of Coimbra, Portugal

A C Singhal Arizona State University, USA


P Skerget University of Maribor, Slovenia
J Sladek Slovak Academy of Sciences,
Slovakia

V Sladek Slovak Academy of Sciences,


Slovakia

A C M Sousa University of New Brunswick,


Canada

H Sozer Illinois Institute of Technology, USA


D B Spalding CHAM, UK
P D Spanos Rice University, USA
T Speck Albert-Ludwigs-Universitaet Freiburg,
Germany

C C Spyrakos National Technical University


of Athens, Greece

I V Stangeeva St Petersburg University,


Russia

J Stasiek Technical University of Gdansk,


Poland

G E Swaters University of Alberta, Canada


S Syngellakis University of Southampton, UK
J Szmyd University of Mining and Metallurgy,
Poland

S T Tadano Hokkaido University, Japan


H Takemiya Okayama University, Japan
I Takewaki Kyoto University, Japan
C-L Tan Carleton University, Canada
E Taniguchi Kyoto University, Japan
S Tanimura Aichi University of Technology,
Japan

J L Tassoulas University of Texas at Austin,


USA

M A P Taylor University of South Australia,


Australia

A Terranova Politecnico di Milano, Italy


A G Tijhuis Technische Universiteit
Eindhoven, Netherlands

T Tirabassi Institute FISBAT-CNR, Italy


S Tkachenko Otto-von-Guericke-University,
Germany

N Tosaka Nihon University, Japan


T Tran-Cong University of Southern
Queensland, Australia

R Tremblay Ecole Polytechnique, Canada


I Tsukrov University of New Hampshire, USA
R Turra CINECA Interuniversity Computing
Centre, Italy

S G Tushinski Moscow State University,


Russia

J-L Uso Universitat Jaume I, Spain


E Van den Bulck Katholieke Universiteit

Z-Y Yan Peking University, China


S Yanniotis Agricultural University of Athens,

D Van den Poel Ghent University, Belgium


R van der Heijden Radboud University,

A Yeh University of Hong Kong, China


J Yoon Old Dominion University, USA
K Yoshizato Hiroshima University, Japan
T X Yu Hong Kong University of Science &

Leuven, Belgium

Netherlands

R van Duin Delft University of Technology,


Netherlands

Greece

Technology, Hong Kong

P Vas University of Aberdeen, UK


R Verhoeven Ghent University, Belgium
A Viguri Universitat Jaume I, Spain
Y Villacampa Esteve Universidad de

M Zador Technical University of Budapest,

F F V Vincent University of Bath, UK


S Walker Imperial College, UK
G Walters University of Exeter, UK
B Weiss University of Vienna, Austria
H Westphal University of Magdeburg,

R Zarnic University of Ljubljana, Slovenia


G Zharkova Institute of Theoretical and

Alicante, Spain

Germany

J R Whiteman Brunel University, UK

Hungary

K Zakrzewski Politechnika Lodzka, Poland


M Zamir University of Western Ontario,
Canada

Applied Mechanics, Russia

N Zhong Maebashi Institute of Technology,


Japan

H G Zimmermann Siemens AG, Germany

Materials Characterisation V
Computational Methods
and Experiments

Editors
A.A. Mammoli
University of New Mexico, USA
C.A. Brebbia
Wessex Institute of Technology, UK
A. Klemm
Glasgow Caledonian University, UK

Editors:
A.A. Mammoli
University of New Mexico, USA
C.A. Brebbia
Wessex Institute of Technology, UK
A. Klemm
Glasgow Caledonian University, UK
Published by
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Computational Mechanics Inc
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Tel: 978 667 5841; Fax: 978 667 7582
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British Library Cataloguing-in-Publication Data
A Catalogue record for this book is available
from the British Library

ISBN: 978-1-84564-538-0
ISSN: 1746-4471 (print)
ISSN: 1743-3533 (on-line)
The texts of the papers in this volume were set individually by the authors or under their
supervision. Only minor corrections to the text may have been carried out by the
publisher.
No responsibility is assumed by the Publisher, the Editors and Authors for any injury and/
or damage to persons or property as a matter of products liability, negligence or
otherwise, or from any use or operation of any methods, products, instructions or ideas
contained in the material herein.
WIT Press 2011
Printed in Great Britain by Martins the Printers.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted in any form or by any means, electronic, mechanical, photocopying,
recording, or otherwise, without the prior written permission of the Publisher.

Preface

The increasing demands for high-quality products from both industry and consumers
are the driving force for the rapid developments in materials science and engineering.
In principle materials science involves relating the desired properties and relative
performance of a material to its microstructural features through characterization.
The major determinants of the structure of a material and hence its properties are
its constituent chemical elements and the way a material has been processed into
its final form.
Over the years, a variety of experimental techniques have been developed for
characterizing the physical and chemical properties of materials. Unfortunately
due to a number of simplifying assumptions and limitations on the use of individual
methods, it is not often possible to describe in a qualitative, reliable way the
microstructural features of many materials. Triangulation of different experimental
methods as well as computer simulations may become essential to achieve a
thorough, comprehensive analysis. Simulations can contribute to the understanding
of the phenomena and to provide a good basis for the development of durable
materials and components which can withstand ambient and extreme environmental
conditions.
The way forward in material characterisation is to develop new experimental
techniques or apply existing methodologies adopted from other related disciplines.
A very wide range of materials, starting with metals through polymers,
semiconductors to composites, necessitates a whole spectrum of experimental
techniques and numerical models, which are specific for material types. Some of
these well established methodologies could potentially find applications in new
fields. In this context a multidisciplinary approach in material characterisation and
the exchange of original ideas is indispensible.
The aim of the International Conference on Computational Methods and
Experiments in Materials Characterisation held in Kos, Greece, was therefore to
facilitate such interdisciplinary interactions within the research community. The

resulting conference book has been arranged in several chapters addressing various
experimental and numerical methods. The wide range of topics covers mechanical
characterisation and testing, corrosion problems and thermal analysis as well as
recycled materials, nano-composites and energy materials.
The editors would like to express their gratitude to all authors without whose
involvement this book could not have been produced. We wish to aknowledge the
valuable input of the members of the Scientific Advisory Committee in attracting
and selecting many high quality contributions. We trust that this book will present
some innovative ideas and will facilitate further developments in materials science.
The Editors,
Kos, Greece 2011

Contents
Section 1: Micro and nano characterisation of cementitious materials
(Special session organised by A. J. Klemm)
Application of positron annihilation lifetime spectroscopy to
nano-characterisation of polymer-modified mortars
P. Guagliardo, A. J. Klemm, S. N. Samarin & J. F. Williams ............................. 3
Multi-technique investigation of calcium hydroxide crystals at the
concrete surface
E. Gueit, E. Darque-Ceretti, P. Tintillier & M. Horgnies ................................. 15
Characterization of the influence of the casting mould on the
surface properties of concrete and on the adhesion of a protective coating
M. Horgnies, P. Willieme, O. Gabet, S. Lombard & M. Dykman...................... 27
Section 2: Nano-materials
HRTEM techniques applied to nanocrystal modeling: towards an
atom-by-atom description
D. G. Stroppa, L. A. Montoro, E. R. Leite & A. J. Ramirez ............................... 41
Ca(OH)2 nanoparticle characterization: microscopic investigation of
their application on natural stones
V. Daniele & G. Taglieri ................................................................................... 55
Nanocarbon composite materials with optical response on
radioactive waste
M. Vantsyan, G. Popova, E. Karpuzova, M. Bobrov, O. Plaksin
& E. Dabek ........................................................................................................ 67

Section 3: Corrosion problems


Evaluation of the fretting corrosion mechanisms on the head-cone interface
of hip prostheses
I. Caminha, C. R. M. Roesler, H. Keide, C. Barbosa, I. Abud
& J. L. Nascimento ............................................................................................ 77
Improving corrosion performance by surface patterning
M. Bigdeli Karimi, V. Stoilov & D. O. Northwood ............................................ 85
Material characterisation to understand various modes of corrosion failures
in large military vehicles of historical importance
A. Saeed, Z. Khan, N. Garland & R. Smith........................................................ 95
Section 4: Computational models and experiments
A multi-factor interaction model (MFIM) for damage initiation
and progression
C. C. Chamis.................................................................................................... 109
Analytical solution of a two-dimensional elastostatic problem of
functionally graded materials via the Airy stress function
H. Sakurai........................................................................................................ 119
Moment curvature analysis of concrete flexural members confined
with CFRP grids
A. Michael & P. Christou ................................................................................ 131
Application of effective media theory in the characterization of the
hygrothermal performance of masonry
Z. Pavlk, E. Vejmelkov, L. Fiala, M. Pavlkov & R. ern......................... 143
3D FIB reconstruction and characterisation of a SOFC electrode
S. Chupin, N. Vivet, D. Rochais & E. Bruneton............................................... 155
Modelling of load transfer between porous matrix and short fibres in
ceramic matrix composites
J. G. P. Silva, D. Hotza, R. Janssen & H. A. Al-Qureshi................................. 165
Modeling aspects concerning the axial behavior of RC columns
H. O. Koksal, T. Turgay, C. Karako & S. Ayenk.......................................... 175

Section 5: Innovative experiments


Surface characterization of eucalyptus and ash wood veneers by
XPS, TOF-SIMS, optic profilometry and contact angle measurements
G. Vzquez, R. Ros, M. S. Freire, G. Antorrena & J. Gonzlez-lvarez........ 187
Interface resistances in heat and moisture transport:
semi-scale experimental analysis
Z. Pavlk, J. Mihulka, J. umr, M. Pavlkov & R. ern ............................. 199
Section 6: Mechanical characterisation and testing
Tension/compression test of auto-body steel sheets with the variation
of the pre-strain and the strain rate
G. H. Bae & H. Huh ........................................................................................ 213
Definition of averaged elastic-plastic characteristics of
sandwich panel structures
I. I. Zakirov, V. N. Paimushin & I. M. Zakirov ................................................ 227
Hot deformation and mechanical properties of P/M Al special
M. Tercelj, P. Cvahte, I. Perus & G. Kugler ................................................... 239
Coarsening kinetics of the bimodal distribution in
DS GTD111TM superalloy
V. S. K. G. Kelekanjeri, S. K. Sondhi, T. Vishwanath, F. Mastromatteo
& B. Dasan ...................................................................................................... 251
Effect of the elastomer stiffness and coupling agents on
rheological properties of magnetorheological elastomers
A. Boczkowska & S. F. Awietjan...................................................................... 263
Optimization of magnetoelastic properties of pure nickel by means
of heat treatments
A. L. Morales, A. J. Nieto, J. M. Chicharro, P. Pintado, G. P. Rodrguez
& G. Herranz................................................................................................... 275
Nanomechanical structure-property relations of dynamically loaded
reactive powder concrete
P. G. Allison, R. D. Moser, M. Q. Chandler, T. S. Rushing, B. A. Williams
& T. K. Cummins ............................................................................................. 287
Dynamic strength of concrete under multiaxial compressive loading
Y. P. Song & H. L. Wang ................................................................................. 299

Modelling and simulation of the rutting resistance of bituminous mixes:


experimental and stochastic approaches
A. E. Ouni, A. Dony & J. Colin........................................................................ 307
Laboratory tests on the cleanliness of soil materials used as subgrades
in pavement structures
A. Athanasopoulou & G. Kollaros................................................................... 315
Use of additives to improve the engineering properties of swelling soils
in Thrace, Northern Greece
A. Athanasopoulou & G. Kollaros................................................................... 327
Characteristics of a bolted joint with a shape memory alloy stud
N. Ould-Brahim, A.-H. Bouzid & V. Brailovski............................................... 339
Section 7: Thermal analysis
Experimental validation of a thermal model of adhesively bonded
scarf repairs for CFRP composite materials incorporating cure kinetics
C. C. N. Bestley, S. G. R. Brown & S. M. Alston ............................................. 351
Computational and experimental characterization of building
envelopes based on autoclaved aerated concrete
V. Ko, J. Vborn & R. ern....................................................................... 363
Section 8: Recycled materials
Quantitative description of the morphology of polyurethane nanocomposites
for medical applications
J. Ryszkowska & B. Waniewski ...................................................................... 377
Description methods of the properties of composites from
oxybiodegradable foil waste and wood
J. Ryszkowska & K. Saasiska........................................................................ 387
The effect of slag composition on recycling of OFHC through the
ESCM process
S. Ketabchi, F. K. Ahadi, K. Hanaee & S. H. Alhoseini .................................. 397
Author Index .................................................................................................. 407

Section 1
Micro and nano
characterisation of
cementitious materials
(Special session organised
by A. J. Klemm)

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Materials Characterisation V

Application of positron annihilation lifetime


spectroscopy to nano-characterisation of
polymer-modified mortars
P. Guagliardo1, A. J. Klemm2, S. N. Samarin1 & J. F. Williams1
1

ARC Centre of Excellence for Antimatter-Matter Studies,


School of Physics, University of Western Australia, Australia
2
School of Built and Natural Environment,
Glasgow Caledonian University, UK

Abstract
Positron annihilation lifetime spectroscopy (PALS) has been applied to study the
microstructural features of immature cement mortars. Two types of cement
mortars containing superabsorbent polymers (SAPs) were studied, in addition to
Ordinary Portland Cement (OPC). The ortho-positronium lifetimes for all
samples were in the range of 1.70-1.73 ns, values that are close to that of free
water (1.7 ns) and hence suggest the presence of water-filled pores. Periodic
lifetime measurements showed that the intensity of this component decreased
slightly over a period of four weeks, indicating water loss associated with the
curing process, evaporation or a combination of the two.
Keywords: cement mortar, superabsorbent polymer, positron annihilation
lifetime spectroscopy, positronium, porosity, hydration, curing.

1 Introduction
Cement is a material of immense practical importance, but in spite of its almost
ubiquitous use, its microstructural characterisation still proves to be problematic.
The complexity of the problem is enhanced when the composition of cement is
modified through the use of auxiliary agents. Ordinary Portland cement is a
combination of gypsum (CS*H2) and clinker. Gypsum acts to prevent rapid
setting of the cement paste while clinker is the hydraulic binder. The major
constituents of clinker are tricalcium silicate (C3S), dicalcium silicate (C2S),
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4 Materials Characterisation V
tricalcium aluminate and tetracalcium alumina-ferrite (C4AF); C = CaO, S =
SiO2, A = Al2O3, F = Fe2O3, S* = SO3 and H = H2O (abbreviations commonly
used in industrial nomenclature) [1, 2].
The presence of water among the active compounds of cement leads to a
rearrangement of their structure and the initiation of the hardening process. The
initial hardening is caused by the hydration of C3S, which forms a gel-like
silicate and calcium hydrate phase referred to as C-S-H gel. These particles
ultimately crystallise and bind together the particles of sand or stone into a hard
mass. Other hydrates of the complexes described above are also formed,
although the reaction rates may differ considerably. The final product is a
hardened cement paste which is a mixture of unreacted cement particles,
hydration products and pores. Two types of pores are usually distinguished capillary pores, which comprise the water- or air-filled spaces between the
hydrates, with sizes in the range of 10-1000 nm, and smaller pores referred to as
gel pores, which are contained in the amorphous hydrate phase. Gel and capillary
pores form a continuous network of pores throughout the material [3, 4].
The mechanical properties of cementitious materials are heavily influenced by
porosity, with the volume and size distribution of pores controlling both the
strength and durability of the material [5]. A detailed characterisation of the pore
structure and the factors that affect it are thus crucial to advancing the design of
these materials; however, classical porosimetry methods such as mercury
intrusion porosimetry (MIP) and gas adsorption cannot always be relied upon to
extract information on pores smaller than a few nanometres [6]. In this regard,
positron annihilation lifetime spectroscopy (PALS) has considerable advantages
over these classical methods. PALS is sensitive to both open and closed porosity,
for example, whereas isolated pores are invisible to the aforementioned
techniques. In addition, PALS is sensitive to pores in the size range of 0.3-30 nm
(that is, in the size range of gel pores), and both pore sizes and relative
concentrations can be measured (refer to the following section for a detailed
explanation) [7]. In this work, PALS was used to study the features of the
porosity of three cement mortars. Two types of cement mortars containing
superabsorbent polymers (SAPs) were studied, in addition to a sample composed
only of OPC.
SAPs are cross-linked networks of hydrophilic polymers with a high capacity
for water uptake - they can absorb and retain up to 500 times their weight in
water. This makes them ideal for use in water-absorbing applications such as
absorbent medical dressings and controlled release media [8]. During the mixing
process the polymers absorb the pore solution immediately after their addition to
the mortar, reaching saturation within minutes [9, 10]. They then swell to form
spherical cavities filled with water. At later stages of the hydration process the
water is released to the concrete matrix and the cavities remain as empty pores.
For mortars with a low water-to-cement ratio, it is possible to replace part of the
irregular capillary pores with larger spherical pores formed by saturated
polymers. The dispersion and size of these pores can be estimated by the
material attributes of polymers.

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Materials Characterisation V

The samples were studied with PALS over a period of 4 weeks with
measurements starting when the samples were aged 21 days, in order to elucidate
the changes in nano-porosity caused by the addition of SAPs as well as the
changes arising from the curing/hydration process. In addition, samples aged at 3
and 6 weeks were studied with MIP to determine changes in their pore
distributions and bulk densities. MIP can provide information on larger pores
(from 100 nm to 100 m) to which PALS is not sensitive.

2 Positron annihilation background


Positron annihilation techniques have been applied to study nano-porosity in a
wide range of materials, such as zeolite, silicates and polymers [7]. In positron
annihilation lifetime spectroscopy (PALS), positrons from a 22Na radioisotope
are injected into the sample under study and a positron lifetime spectrum is
recorded [11]. As a 1.274 MeV gamma-quantum is emitted during the decay of
22
Na almost simultaneously with a positron, the lifetime is defined as the time
between detection of the 1.274 MeV photon and the subsequent 511 keV photons
created from the positrons annihilation with an electron. The measured spectrum
is a histogram of the time periods between these two events. Ideally, it is a sum
of decaying exponentials of the form

(1)

positron state with lifetime . An


where is the intensity or weighting of the
experimentally obtained spectrum differs from this form however, in that it is
convolved with the time response function of the apparatus, usually
approximated by a sum of Gaussians.
Porosimetry is made possible by exploiting the phenomenon of positronium
(Ps) formation, Ps being the hydrogen-like bound state of a positron and an
electron [12]. In brief, positrons penetrate the material under investigation and
rapidly lose energy, predominately through ionising collisions. Ps formation can
then take place as a reaction between the positron and a secondary electron
produced during the positrons thermalisation (these secondary electrons are
often termed spur electrons [13]). Positronium is formed in two spin states with
dramatically different annihilation characteristics. The singlet state (with antiparallel orientation of spins) is termed para-positronium (p-Ps); it has a vacuum
lifetime of 125 ps and decays via the emission of two gamma quanta. The triplet
state (with parallel spins of electron and positron) is referred to as orthopositronium (o-Ps) and has a much longer vacuum lifetime of 142 ns, decaying
via three gamma emission. Due to its short lifetime, p-Ps is not significantly
perturbed by the material; however, o-Ps, because of its intrinsically longer
lifetime, interacts strongly with the material and its pore structure. In the
presence of matter, o-Ps can decay into two gammas via a process known as
pick-off annihilation - the positron in o-Ps annihilates with an electron of
opposite spin in the material via a two-gamma process. As a result of pick-off
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6 Materials Characterisation V
annihilation, the o-Ps lifetime in matter is significantly shorter than its vacuum
value (and can be as low as ~ 1 ns) [7].
The basis for studying porosity is that o-Ps tends to localise in regions of low
density, such as pores. This is because in the bulk of the material the positron
and the electron in o-Ps experience repulsive Coulomb and exchange forces
respectively. As a result, most of these materials (porous insulators) have a
negative work function for positronium [7]. Porosimetry is possible because the
annihilation rate (the inverse of the lifetime) in the pore is a function of the pore
size smaller pores have a shorter lifetime compared to large pores, where the
overlap of the Ps wave function with the pore walls is reduced. A semi-empirical
quantum mechanical relation has been developed by Tao [14] and Eldrup et al.
[15] to relate the o-Ps lifetimes to pore radii:
1

= 2 1-

R
R+R

1
2

sin

2R

(2)

R+R

where is the lifetime, R+R is the pore radius and R is empirically


determined to be 0.16-0.17 nm. This model is applicable to sub-nanometre pores
of a spherical geometry. Gidley et al. [16, 17] extended this model to include
larger pore sizes and varying pore geometries (cylinders, cubes, channels and
sheets).

3 Experimental
3.1 Materials and mixes
For the purpose of this research Portland cement (BS EN 197-1 CEM II/B-V
32,5) was mixed at 1:1 ratio with fine sand (the vast majority of particles were
distributed below 0.6 mm). Throughout the investigation the total water-tocement ratio of 0.45 was maintained. The mix compositions are presented in
Table 1. The pastes were shaped into cylinders with diameters of about 25 mm
and thicknesses in the range of 5-10 mm.
Table 1:

Composition of cement mortars.

Sample designation

OPC

SAP-A

SAP-B

Mix code

(Water/Cement)total

0.45

0.45

0.45

(Water/Cement)effective

0.45

0.425

0.438

Sand/Cement

SAP content [%] (by cement weight)

0.25

0.25

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Materials Characterisation V

The SAPs used in this study were cross-linked polymers provided by BASF.
SAP-A is a copolymer of acrylamide and acrylic acid and SAP-B is a polymer
based on acrylic acid. The products had absorption capacities of 200-250 ml/g in
demineralised water, though the absorption in mortar depended on the product
and was approximately 10 mL/g for SAP-A and 5 mL/g for SAP-B. Both
materials were prepared by grinding and screening to sizes of 63-125 m, but
there was also a minor (less than 10%) content of finer particles. The SAP
particle shapes were irregular and their sizes after initial absorption were in the
range of 135-270 m for SAP-A and 105-210 m for SAP-B.
3.2 Positron lifetime and mercury intrusion measurements
For positron lifetime measurements, approximately 30 Ci of 22NaCl was
deposited on 7m Kapton foil and covered with an identical foil. The edges of
this foil-sandwich were then sealed, and this source foil was placed between two
identical pieces of sample. The positron lifetimes were measured with a fast-fast
coincidence system. The gamma-ray detectors consist of a truncated cone (31.8
mm diameter tapering to 12.7 mm with a height of 12.7 mm) BC418 scintillator
coupled to a Burle 8850 photomultiplier tube. The time resolution of the system
is approximately 220 ps, as determined from analysis of a spectrum of highpurity annealed nickel. The spectra comprise of at least 2 million counts and
have been analysed using PAScual version 1.3.0 [18].
Mercury intrusion porosimetry (MIP) has been carried out with the use of a
Porosimeter Autopore IV 9500 by Micromeritics, with a pressure range up to
60000 psi for all samples at ages 3 and 6 weeks.

4 Results and discussion


In Table 2 the fitted lifetimes and intensities for all samples are given at four
different ages. In each case, the lifetime spectra could be fitted with three
discrete components. In porous media a number of annihilation processes are
possible because multiple positron and positronium states exist. It is likely that
the two shorter lifetime components (1 and 2) in Table 2 are the averages of
several different annihilation modes. These could include positron annihilation
(of both free and trapped positrons), p-Ps self-annihilation and o-Ps pick-off
annihilation in the bulk of the material, and annihilations in the source foil.
Nanosecond lifetime components (3) on the other hand are typically
associated with o-Ps pick-off annihilation in nano-pores. For all of the cement
samples the average 3 over the course of the measurements was in the range of
1.70-1.73 ns. The presence of a nanosecond component is often an indicator of
porosity or free volume, and these values would correspond to pores having
diameters in the range of 0.51-0.52 nm (using the TE model, equation 2).
However, these lifetimes are very close to that observed in pure water,
approximately 1.7 ns [19]. Given that cement pastes are known to contain a
significant fraction of water, and that the samples were tested at a relatively
young age (testing began at 21 days after mixing), it seems likely that these
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8 Materials Characterisation V
nanosecond components are associated with annihilation in water contained in
capillary pores of the cement and hence cannot be directly related to a pore size.
Consolati and Quasso [20, 21], Consolati et al. [22] and Salgueiro et al. [23]
observed similar lifetimes in Portland cement pastes and attributed this
component to water-filled pores.

OPC

SAP-B

SAP-A

Table 2:
Age
(weeks)
3
4
5
6
3
4
5
6
3
4
5
6

Lifetimes and intensities; standard deviations are given in brackets.


1 (ps)

2 (ps)

218 (9)
227 (9)
242 (7)
233 (8)
219 (5)
229 (5)
221 (6)
237 (6)
224 (6)
239 (5)
238 (5)
212 (9)

410 (10)
410 (10)
430 (10)
420 (10)
409 (7)
421 (9)
409 (8)
420 (10)
402 (8)
430 (10
420 (10)
390 (10)

3 (ns)

I1 (%)

I2 (%)

I3 (%)

1.67 (0.02)
1.67 (0.03)
1.73 (0.03)
1.72 (0.03)
1.73 (0.02)
1.76 (0.03)
1.71 (0.03)
1.63 (0.03)
1.71 (0.02)
1.67 (0.02)
1.67 (0.03)
1.73 (0.03)

43 (4)
46 (5)
55 (4)
50 (4)
45 (2)
49 (3)
46 (3)
53 (4)
47 (3)
57 (3)
53 (3)
43 (3)

50 (3)
48 (5)
40 (4)
44 (4)
49 (2)
46 (3)
50 (3)
43 (4)
48 (3)
39 (2)
42 (3)
53 (4)

5.9 (0.1)
5.7 (0.2)
5.2 (0.2)
5.2 (0.2)
5.0 (0.1)
4.0 (0.1)
4.3 (0.1)
4.2 (0.2)
4.6 (0.1)
4.3 (0.1)
4.2 (0.1)
4.3 (0.1)

0.93
1.04
0.99
0.99
1.15
1.08
1.04
1.08
1.01
1.01
1.09
1.07

In Figure 1, o-Ps lifetimes (3) and intensities (I3) are plotted as a function of
sample age. Lifetime spectra were recorded every 7 days for a 4 week period.
Over the course of the measurements, I3 for the cement sample containing SAPA is somewhat higher than for the cement containing SAP-B and the pure
cement sample. If these lifetimes are indicative of water-filled pores then this
suggests a higher concentration of pores in the sample containing SAP-A. As the
results for SAP-B are closer to those of pure cement, this suggests that the
presence of the polymer does not significantly alter the pore concentration.
For the SAP-A sample, a gradual decrease in I3 is observed over weeks 3-5,
whereas for the SAP-B and pure cement samples there is a decrease after the
initial measurement (weeks 3-4), and then I3 is relatively constant. While these
changes are small, they may be indicative of various stages of the hydration
process, as the decrease in I3 is consistent with the reduction in total porosity that
is known to occur as hydration progresses [3]. The gradual decline seen in the
SAP-A sample suggests that this polymer releases its water more slowly
compared to SAP-B.
At the onset of the measurement (age 21 days) the hydration process is likely
to be still underway, with both di- and tri-calcium silicates reacting with water to
produce a network of calcium silicate hydrates. Water could then be consumed in
the hydration process for at least the next two weeks. However, during this time
it is difficult to say if the loss of water seen by the decrease in I3 is also
associated with evaporation. As the samples lose water one might expect the
lifetimes to increase as there would be a transition from filled to empty pores.

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Materials Characterisation V

The fact that this does not occur suggests that pores collapse with water loss (the
volume of capillary pores is known to decrease with hydration [3]).
These results are consistent with the work of Consolati and Quasso [20, 21]
who observed a systematic decrease in I3 with sample age, but they are in
contrast to the work of Myllyl and Karras [24] where the opposite trend was
seen. It should be noted however that a direct comparison with these studies is
not possible due to differing experimental conditions (namely the composition
and age of samples).

o-Ps intensity, I3 (%)

6.5
6.0
5.5
5.0
4.5
4.0
3.5
3

Sample age (weeks)

o-Ps lifetime, 3 (ns)

2.2
2.0
1.8
1.6
1.4
1.2
3

Sample age (weeks)


Figure 1:

o-Ps intensities (top) and lifetimes (bottom) vs. sample age for
SAP-A (circles), SAP-B (triangles) and Ordinary Portland Cement
(squares).

In addition to PALS, MIP measurements were carried out on samples aged 3


and 6 weeks; the resulting pore distributions are shown in Figure 2. It is apparent
that the samples contain a wide distribution of pores, with the majority of pores
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10 Materials Characterisation V

0.25
0.2
0.15
0.1
0.05
0
1000000 100000

10000

1000

100

10

Log differential intrusion (mL/g)

in the size range of 10-100 nm. The MIP results are in qualitative agreement with
the PALS data in the sense that the sample containing SAP-B displays similar
behaviour to pure cement - at 6 weeks their pore distributions almost coincide
and the total porosity for both samples has decreased with aging. This decrease is
also consistent with the reduction in I3 seen in the PALS data.

0.25
0.2
0.15
0.1
0.05
0
1000000 100000

10000

1000

100

10

Log differential intrusion (mL/g)

Pore size diameter (nm)

Pore size diameter (nm)


Figure 2:

Pore size distributions determined by MIP at age 3 weeks (top) and


6 weeks (bottom); OPC diamonds, SAP-A squares, SAP-B
triangles.

Conversely, the SAP-A sample shows a significant increase in the pore


concentration within the 10-100 nm range at 6 weeks. This is in contrast to the
decrease in I3 seen in PALS, although PALS may not be sensitive to the porosity
in this size range. In spite of the differing trend, both PALS and MIP show that
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Materials Characterisation V

11

the presence of SAP-A significantly alters the hydration process of the cement
mortar.
The bulk densities of the samples were also determined by MIP
measurements (Table 3). It was found that the density of all samples increased
with aging time. Again, the changes in density for the pure cement and SAP-B
samples are similar. The change in density for SAP-A is much smaller, which is
consistent with the slower rate of change of I3.
Table 3:
Sample
OPC
SAP-A
SAP-B

Bulk densities determined by MIP at 3 and 6 weeks.


Bulk density at 3 weeks
(g/mL)
1.83
1.82
1.84

Bulk density at 6 weeks


(g/mL)
1.89
1.86
1.91

In order to gain further insight into the nature of the porosity, the samples
were heated at 116C for 4 hours under vacuum conditions (10-5 Torr) and
lifetime measurements were repeated. Lifetime spectra were recorded directly
after heating and the samples were sealed in a plastic bag containing a desiccant
(to prevent water absorption) during the measurement. The resulting lifetimes
and intensities are given in Table 4 and the corresponding pore sizes are given in
Table 5.
At least three types of water can be distinguished in a hydrating cement paste.
Chemically-bound water is directly incorporated into the structure of the
hydration products, physically-bound water is absorbed on the surfaces of
cement particles and reaction products, and there is also free water contained
in the capillary and gel pores [25]. The heat treatment will have removed a
significant fraction of the latter two sources of water; however, much higher
temperatures (above 950C) are required to remove chemically-bound water.
Table 4:

Lifetimes and intensities obtained after heat treatment.

1 (ps)
2 (ps)
3 (ns)
4 (ns)
I1 (%)
I2 (%)
I3 (%)
I4 (%)
2

OPC
263 (2)
536 (7)
4.3 (0.1)
75 (2)
24 (1)
1.3 (0.1)
1.13

Sample
SAP-A
214 (9)
380 (9)
1.32 (0.07)
12.6 (0.7)
36 (8)
60 (7)
3.3 (0.4)
1.0 (0.1)
1.05

SAP-B
219 (4)
413 (5)
1.62 (0.05)
14.9 (0.6)
44 (2)
52 (2)
2.5 (0.1)
0.70 (0.01)
1.01

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12 Materials Characterisation V
After heat treatment, 3 for OPC increases to 4.3 ns. This corresponds to a gel
pore diameter of 0.86 nm using the TE model (equation 2). However, the
intensity of this component decreases by a factor of about 3.3; this could suggest
that a significant fraction of the pores collapse upon water removal. There is also
a significant redistribution of intensity from I2 to I1 after heat treatment. These are
the shorter components associated with multiple positron states in the material.
The redistribution of intensity from the longer component (2) to the shorter one
(1) indicates that the heat treatment has reduced the number of positron traps in
the bulk material. This could be associated with an increase in the bulk density
after heating.
Table 5:

Pore diameters, d3 and d4, calculated from o-Ps lifetimes, and total
o-Ps intensities (Io-Ps).

d3 (nm)
d4 (nm)
Io-Ps before (%)
Io-Ps after (%)

OPC
0.86
4.3
1.3

Sample
SAP-A
0.42
1.45
5.2
4.3

SAP-B
0.50
1.56
4.2
3.2

For the cement samples containing SAPs an additional low intensity, long
lifetime component (4) appears in the spectra after heat treatment (and due to
the presence of this long component it was necessary to fix the background to the
left of the main coincidence peak to the average value in the analysis). 4 may be
associated with pores formed by the polymers which have replaced some of the
ordinary pore structure, and its emergence shows that the presence of SAP
significantly alters the structure of the cement paste.
For the sample containing SAP-A, 3 = 1.32 ns and 4 = 12.6 ns, with
respective intensities of 3.3% and 1.0%. These lifetimes would correspond to
pores having diameters of 0.42 and 1.45 nm respectively. There is also a
redistribution of the weighting of the shorter components (1 and 2); however
this is not as pronounced as for ordinary Portland cement.
For the sample containing SAP-B, 3 = 1.62 ns and 4 = 14.9 ns, with
intensities of 2.5% and 0.7% respectively. These lifetimes correspond to pores
having diameters of 0.42 and 1.45 nm respectively. The value of 3 is comparable
to that obtained before heat treatment (which was similar to the o-Ps lifetime in
water). This could suggest that the heat treatment did not result in the complete
removal of free water.
For both SAP-A and SAP-B the total o-Ps intensity (I3 + I4) decreases after
heat treatment, signalling a reduction in porosity; however, the reduction is
larger for the ordinary Portland cement sample.

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Materials Characterisation V

13

5 Conclusion
This study has shown that PALS can be used to monitor the hydration process in
cement samples by using the o-Ps intensity as an indicator of the concentration
of water-filled pores. In addition, PALS has shown that the addition of a SAP to
the cement mixture alters the structure and hydration process of cement. The
addition of SAP-A caused the hydration process to progress more gradually
compared to OPC; however, the addition of SAP-B gave comparable results to
that of OPC.
Both PALS and MIP showed that the presence of SAP-A has a significant
effect on the hydration process. In addition, MIP showed that the concentration
of pores in the 10-100 nm range increases with aging for the SAP-A sample.
For the samples with SAP added, heat treatment under evacuation (resulting
in the removal of free water) gave rise to an additional long lifetime component
and a higher overall o-Ps intensity compared to OPC. This shows that the SAP
had modified the pore distribution, replacing some of the regular pore
distribution with larger pores formed by saturated polymers.

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14 Materials Characterisation V
[15] Eldrup, M., Lightbody, D. & Sherwood, J. N. The temperature dependence
of positron lifetimes in solid pivalic acid. Chemical Physics 63, 51-58,
(1981).
[16] Gidley, D. W. et al. Positronium annihilation in mesoporous thin films.
Physical Review B 60, R5157 (1999).
[17] Gidley, D. W. et al. Determination of pore-size distribution in lowdielectric thin films. Applied Physics Letters 76 (2000).
[18] Pascual-Izarra, C. et al. Advanced fitting algorithms for analysing positron
annihilation lifetime spectra. Nuclear Instruments and Methods in Physics
Research Section A: Accelerators, Spectrometers, Detectors and Associated
Equipment 603, 456-466, (2009).
[19] Patro, A. P. & Sen, P. Anomalous parapositronium lifetime in water at 20
degrees C. Journal of Physics C: Solid State Physics 5, 3273 (1972).
[20] Consolati, G. & Quasso, F. Evolution of porosity in a Portland cement paste
studied through positron annihilation lifetime spectroscopy. Radiation
Physics and Chemistry 68, 519-521 (2003).
[21] Consolati, G. & Quasso, F. A positron annihilation study on the hydration
of cement pastes. Materials Chemistry and Physics 101, 264-268 (2007).
[22] Consolati, G., Dotelli, G. & Quasso, F. Positron lifetime spectroscopy as a
probe of nanoporosity of cement-based materials. Radiation Physics and
Chemistry 58, 727-731 (2000).
[23] Salgueiro, W., Somoza, A., Cabrera, O. & Consolati, G. Porosity study on
free mineral addition cement paste. Cement and Concrete Research 34, 9197, (2004).
[24] Myllyl, R. & Karras, M. Positron Annihilation Probing for the Hydratation
Rate of Cement Paste. Applied Physics 7, 303-306 (1975).
[25] Sen Wang, P. U. et al. 1H nuclear magnetic resonance characterization of
Portland cement: molecular diffusion of water studied by spin relaxation
and relaxation time-weighted imaging. Journal of Material Science 33,
3065-3071 (1998).

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15

Multi-technique investigation of calcium


hydroxide crystals at the concrete surface
E. Gueit1, E. Darque-Ceretti1, P. Tintillier2 & M. Horgnies2
1

MINES ParisTech, Center for Material Forming, Sophia Antipolis,


France
2
Lafarge Centre de Recherche, St Quentin Fallavier, France

Abstract
The durability and aesthetic qualities of high-performance concrete, which
makes it particularly suitable for architectural applications, are constantly
compromised by environmental aggressions. In this study, an innovative solution
was developed to protect the concrete from these aggressions, which consists of
growing a mineral coating on the concrete surface. The coating is composed of
layered calcium hydroxide crystals, whose nucleation and growth are triggered
byvarious non-ionic surfactants (the details of the process will not be presented).
This paper describes the procedure used to investigate the structure of the formed
crystals. Scanning Electron Microscopy and optical microtopography were used
to determine the morphology of the crystals. Image analysis allowed the
quantification of their amount, size and shape. The contribution and limits of
each technique are discussed.
Keywords: concrete, scanning electron microscopy, image analysis, optical
microtopography, surface.

1 Introduction
The mechanical and aesthetic durability of concrete is often compromised by the
constant environmental aggressions to which the structures are exposed (organic
or inorganic particles, algae, micro-organisms, staining from various sources). It
is possible to protect concrete from these attacks and increase its durability by
applying organic coatings on the hardened surface, but this comes with
operational and environmental costs.

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16 Materials Characterisation V
An innovative solution was proposed [1], which consists on covering and
protecting high-performance concrete (HPC) with a mineral coating made of
calcium hydroxide crystals (CH). The crystals growth happens during the
concrete setting and is triggered by the presence of non-ionic surfactants at the
concrete/formwork interface. One of the difficulties of this study was to
determine the adequate characterization methods to properly investigate the
influence of various surfactants on the amount, morphology and size of the
crystals. Several techniques exist to observe, measure and study concrete
hydrates, but not all of them are directly suitable for surface investigation.
An original procedure had to be developed, combining several techniques.
The structure and morphology of the crystals were assessed through Scanning
Electron Microscopy (SEM) both on the concrete surface and on polished
section. The SEM observations were completed by microtopography on the
concrete surface. The quantification of the amount and size of the crystals was
made by image analysis on binocular images of the concrete surface. The
purpose of this paper is to illustrate what each of these techniques can bring to
concrete surface studies.

2 Morphology of the crystals


The most common method to observe concrete hydrates morphology is Scanning
Electron Microscopy [2]. Most of the time, the observations are made on
polished section in secondary electron mode. When higher magnifications or no
polishing are required, fresh fractures can also be observed. Surprisingly, it is
very rare to find published picture of concrete surface directly observed by SEM.
In this study, SEM observations were conducted on both surfaces and crosssections of the concrete. Small cubes (1 cm x 1 cm x 1 cm) were cut from each
concrete sample. For surface observation, the cubes were directly carbon-coated
on the adequate face and observed in secondary electron mode. For crosssections observations, the cubes were impregnated, polished and carbon-coated,
and then observed in back-scattered electron mode. A SEM FEG Quanta 400
from FEI Company was used at an accelerating voltage of 15kV and current
intensity of 1mA.

Figure 1:

SEM observations of a standard high-performance concrete surface


in secondary electron mode (A) and in back-scattered electron
mode on a polished section (B).

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Materials Characterisation V

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Figure 1 shows observations of both the surface (A) and the cross-section (B)
of a standard high-performance concrete. No specific features are visible on the
surface, except for a couple of scratch due to the formwork defects. As for the
polished section, it reveals a classical concrete microstructure, with dark grey
aggregates and light grey un-hydrated cement grains surrounded by cement
paste.
Figure 2 shows SEM observation of two cross-sections from two different
samples. These observations reveal the presence at the concrete surface of a thin
layered structure presenting various orientations and organization, sometimes
well-aligned parallel to the surface (A), sometimes arranged in a more chaotic
way in the first micrometers of the surface (B). At this level of observation, it is
not possible to clearly indentify the nature of this unexpected phase. The limited
magnification in back-scattered mode, the thin structure of the hydrates and the
surface damages due to the polishing all complicate the interpretation. This is
why it is necessary to make complementary observations of the surface itself.

Figure 2:

SEM observation in back-scattered electron mode of two polished


sections from two different concrete samples from the study.

Figure 3 shows the same samples as figure 2 observed from the surface in
secondary electron mode. These micrographs allow a better understanding of the
structure of the crystals. All of them share the same layered and flaky structure
with different orientations. In all cases, the crystals are composed of thin leaves
that grow around the nucleation point. For some crystals, these leaves are strictly
parallel to the surface and grow as flower petals around the central point,
reaching sometimes a perfect hexagonal shape. For other crystals, the leaves are
strictly perpendicular to the surface, forming a very regular spherulitic structure.
This very organized structure was not visible on the polished sections, where the
leaves appeared randomly implanted in the surface. This is due to the polishing,
which damaged the first micrometers of the surface and disturbed the structure.
The characteristic hexagonal shape of the crystals, as well as their layered
organization, allow identifying them as calcium hydroxide no other concrete
phase would present this morphology. This is confirmed by EDS analysis, where
mostly calcium is detected is these areas (spectrum not showed).
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18 Materials Characterisation V

Figure 3:

SEM observation in secondary electron mode of the surface of two


different samples from the study.

3 Amount and size of the crystals


3.1 Microtopography
SEM observations were very useful to highlight the presence of an unusual phase
and to identify it as CH crystals, but they are not sufficient to get a complete
insight on the structure of the crystals. Even though the secondary electrons give
information on the surface topography, it is difficult to evaluate from the
micrographs how thick the crystals are or how deep they are embedded in the
surface. As for the polished section, the crystals layers are too strongly
delaminated by the polishing for the observation to be conclusive. This is why
the observations were completed with profilometry of the surface. Mechanical
and optical profilometry are sometimes used on concrete to assess its roughness
and evaluate its behavior regarding adhesion problems [35].
In our case, the measurements were made using optical profilometry only,
because a mechanical probe is likely to damage the very fragile CH crystals. The
measurements were made on a confocal full-field 3D surface profilometer with a
spot of 2 micrometers and a working distance of 4.5 mm. In these conditions, the
vertical resolution is 0.01 micrometers and the lateral resolution 0.1 micrometer.
Areas of 4 x 4 mm were scanned with a step of 10micrometer. The data were
computed using the software MountainsMap. In the examples given below, there
were only two steps of data treatments: the maps were straightened to
compensate for the horizontality defects, and profiles were extracted.
Figure 4 shows an example of profilometry on a sample where the crystals are
oriented preferentially parallel to the surface. Two patterns appear on the 2D
mapping: regular and slightly curved lines, which are due the formwork texture,
and irregular spots, which are the CH crystals. Below the mapping is a roughness
profile extracted along the dotted line. The narrow peaks correspond to the lines,
the larger one at 1.7 mm corresponds to the CH crystal in the middle. The profile
allows measuring the size of the crystal (400 micrometers) and the height
between the concrete surface and the top of crystal (5 micrometers).
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Figure 4:

Example of a mapping of the concrete surface. The profile was


extracted from the mapping along the black dotted line.

Figure 5:

Example of a mapping of the concrete surface. The profile was


extracted from the mapping along the black dotted line.

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20 Materials Characterisation V
The same measurements can be made of figure 5. The mapping was acquired
on the same sample, but in an area were the CH crystals have been pulled out of
the surface during the demoulding phase, leaving hollows the size of the crystals.
The depth of the hollows gives the height between the surface and the bottom of
the crystals.
The measurements from figures 4 and 5 give an estimation for the total
thickness of the crystals of 20 micrometers. Of course, the operation has to be
repeated a large number of times to obtain statistical results. This is only one
example taken from one of the samples.
It should be noted that profilometry gives no conclusive information for the
samples where the crystals are oriented perpendicular to the surface. Figure 6
shows a mapping of such a sample (A): the spherulitic structures appear slightly
lighter than the surface, but are difficult to distinguish. A zoom on the mapping
(B) reveals that the crystals are indeed apparent, but that the resolution is far
from being sufficient to separate the different flakes composing the structure.

Figure 6:

Example of a mapping from a sample with perpendicular crystals.


The 3D mapping on the right is a zoom from the 2D mapping on
the left.

3.2 Image analysis


The only way to know the amount of CH crystals as well as their dimension and
geometrical parameters is to count and measure them one by one. Image analysis
software are capable of automatically achieve this procedure on a large number
of images, provided that they are correctly settled by the operator.
Image analysis has been successfully used in previous studies [2, 6] to assess
the amount of calcium hydroxide in concrete as well as the geometrical
parameters of the particles (size, shape, etc.). In those cases, image analysis was
conducted on SEM micrographs from polished sections.
In our case, there is no need to work on sections as the crystals are on the
concrete surface. Furthermore, the crystals are so large that SEM micrographs
are not suitable for a proper counting. Even at low magnification, there are too
few particles in the observation field. On the contrary, images taken under a
binocular have the right scale to count and measure the particles.
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The CH crystals are shinier than the cement paste, which makes them visible
with the naked eye, but this is not sufficient for image analysis software to
distinguish them. To overcome this problem, the samples were coloured with a
black felt-tip pen prior to analysis. The black ink penetrates the cement paste,
strongly colouring it, but is not absorbed by the crystals which then become
clearly distinguishable.
For each concrete samples, five small areas of the surface (1 cm2) were
coloured and photographed under a binocular. The images were treated and
analysed using the open-source software ImageJ [7].
The most difficult step in image analysis is to separate the studied particles
from the background. In our case, the following procedure was used.
Figure 7 shows an example of an image prior to treatment. The brightness and
contrast of the images were optimized using the automatic function on the
software. The optimization was not based on the whole image, but on the
histogram analysis of a small area of one of the particle on the image. This step
created a highly contrasted image where particles appeared red and the
background black (figure 8).

Figure 7:

Figure 8:

Example of an image before treatment by the software imageJ.

Example of an image after optimization of the contrast and


brightness.

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22 Materials Characterisation V
The noise was removed using the remove outliers function of the software,
which replaces each pixel by the median value of its neighbours in a given area
(figure 9). In this case, a radius of 20 pixels was considered, and the removing
was set to occur if the difference between the considered pixel and the median of
its neighbour was higher than 10.

Figure 9:

Example of an image after noise removal.

The images were then converted to binary and inverted. At this point, the
background appeared white and the particles black (figure 10).

Figure 10:

Example of an image after conversion to binary.

The holes in the particles were closed using the Fill holes function of the
software (figure 11).
Finally, the watershed function was used to automatically draw the outlines
of the particles (figure 12). This step might be the main cause of errors in the
measurements, as watershed segmentation works best for convex objects that do
not overlap too much. In some cases, the software was not able to correctly
separate clusters of particles, which were then counted as one big particle.

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Materials Characterisation V

Figure 11:

Figure 12:

23

Example of an image after filling the holes.

Example of an image after the software automatically delimited the


particles.

Once the image was treated, the particles were counted one by one. The
smallest ones (with a surface smaller than 0.1 mm) were not considered as they
are more likely residual noise than actual crystals. The particles overlapping with
the boarder of the image were not considered either as their size would not be
correctly measured. This means than the measured amount of crystals (from 1 to
20 particles per mm depending on the samples) is slightly smaller than reality.
The following parameters were measured for each particle:
- The coordinates of the centre of the particles. These coordinates were
used to calculate the distance between each crystal and its closest
neighbour and to verify that the nucleation appeared randomly and
homogeneously on the surface (figure 13).
- The Ferets diameter, which is the longest distance between two
opposing points of the particle.
- The fraction area of the surface covered by the crystals. As these
crystals are artificially grown to act as a mineral coating, this fraction
area must be as high as possible. The results showed that even if the
crystals seemed very large, they hardly cover 50% of the surface, except
in one promising case where almost 100% of the surface was coated.
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24 Materials Characterisation V
-

The circularity of the particle, which is defined by 4.area / perimeter.


A perfect circle has a circularity of 1, whereas a very elongated particle
has a circularity close to 0 (figure 14). This geometrical parameter is
very convenient to distinguish the crystals that grow parallel to the
surface with regular shapes (high circularity) from the crystals that grow
perpendicular to the surface, which have a low circularity.

Figure 13:

Example of spatial distribution of the particles on the concrete


surface, showing that the nucleation occurs rather homogeneously
on the surface.

Figure 14:

Two examples of the circularity distribution. The curve marked


with squares corresponds to a sample where the crystals have a low
circularity because they grow perpendicular to the surface. The
curve marked with dots corresponds to a sample where the crystals
have a high circularity because they grow parallel to the surface
and adopt very regular shapes.

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The results of the image analysis allowed a better understanding of the


influence of various surfactants on the nucleation (amount of particles) and
growth (size and orientation of the particles) of the CH crystals.
Two types of sample could not be properly analyzed though, one because it
exhibited excessive roughness that induced too much background noise on the
images, and one because the crystals overlapped too much to be clearly
separated. In those cases, a more sophisticated procedure has to be developed. In
particular, software capable of separating overlapping particles exists, but they
were not tested yet in this study.

4 Conclusion
Three techniques scanning electron microscopy, microtopography and image
analysis were successfully used to assess the morphology and geometrical
parameters of calcium hydroxide crystals at the concrete surface. These
techniques are well-known and developed, but not necessarily widely used in
concrete research. Yet, they have proved very efficient in this case to make a
preliminary study of a new phenomenon the massive growth of CH crystals in
presence of surfactants, bringing complementary information and results. Of
course, they absolutely do not make further investigation any less necessary. For
example, a proper crystallographic study would be essential to fully understand
the growing mechanisms and the action of the surfactants.
In the field of materials characterization, it is important to be creative and to
combine and adapt existing techniques. This is particularly true in the field of
concrete research, and even more when it comes to concrete surface, a topic
which is slowly emerging and where a lot of fascinating research still waits to be
done.

References
[1] Gueit, E., Darque-Ceretti, E., Tintillier, P. & Horgnies, M., Surfactantinduced growth of calcium hydroxide at the concrete/formwork interface as
a mineral coating for concrete, Manuscript submitted for publication.
[2] Skalny, J., Gebauer, I. & Odler, I., (eds). Calcium Hydroxide in Concrete,
The American Ceramic Society: Westerville, 2001.
[3] Garbacz, A., Courard, L., & Kostana, K., Characterization of concrete
surface roughness and its relation to adhesion in repair systems, Materials
Characterization, 56, pp. 281-289, 2006.
[4] PER09 Perez, F., Bissonette, B. & Courard, L., Combination of mechanical
and optical profilometry techniques for concrete surface roughness
characterisation. Magazine of Concrete Research, 61(6), pp. 389-400, 2009.
[5] Ramirez, A.M., Demeestere, K., De Belie, N., Mntyl, T., & Levnen,
E, Titanium dioxide coated cementitious materials for air purifying
purposes: Preparation, characterization and toluene removal potential,
Building and Environment, 45, pp. 832-838, 2010.

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26 Materials Characterisation V
[6] Gallucci, E. & Scrivener, K., Crystallisation of calcium hydroxide in early
model and ordinary cementitious systems, Cement andConcrete Reseach,37,
pp. 492-501, 2007.
[7] NIH, http:\\rsbweb.nih.gov/ij

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Characterization of the influence of the casting


mould on the surface properties of concrete
and on the adhesion of a protective coating
M. Horgnies, P. Willieme, O. Gabet, S. Lombard & M. Dykman
Lafarge Centre de Recherche, St Quentin-Fallavier, France

Abstract
Protective coatings are deposited on concrete to improve aesthetics and to
prevent ageing. However, their adhesion on concrete depends on several
interlinked parameters. In this study, the surfaces of concrete are characterized
according to the process of casting and post-treatment used (sandblasting) by
using Scanning Electron Microscopy (SEM), Fourier Transformed-Infrared (FTIR) spectroscopy and profilometry. The surface properties are correlated to the
adhesion force of a polyurea (PU) coating. The development of a specific peel
test (a strengthened and porous membrane is introduced into the layer of liquid
coating before its crosslinking) ensures a reproducible debonding of the
coating/concrete system and allows measuring the fracture energy. Moreover, the
interface after debonding is analyzed by FT-IR to highlight the presence of
concrete/coating residues and to determine the locus of failure. Results underline
that the nature of casting mould influences the concrete surface and modifies the
adhesion of PU coating. The mould made of polyoxymethylene (POM) induces a
micro-tearing of the extreme surface of concrete during demoulding. By
increasing the roughness and the open porosity of the concrete surface, this
tearing enhances the adhesion of the coating. On the contrary, the smooth
concrete surface, induced by the use of a polyvinylchloride (PVC) mould,
decreases the anchorage of the coating. Finally, the sandblasting of the surface,
by increasing the roughness and the interface area, is an interesting treatment to
promote the adhesion of PU coating, whatever the mould used for the casting.
Keywords: concrete, coating, roughness, FT-IR, SEM, peel test, adhesion.

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28 Materials Characterisation V

1 Introduction
The staining of concrete could occur due to its specific microstructure that
retains the liquid and dust particles. The deposition of a coating is then important
to close the surface porosity and protect concrete against acid rains, settlement of
algae and lichensetc [1, 2]. PU coatings are commonly used due to their high
resistance against chemical and mechanical aggressions [3, 4]. However, the
surface properties of concrete depend on several interlinked parameters as
chemical composition, intrinsic porosity and roughness. The aim of this study
concerns the influence of the casting process and post-treatment on the adhesion
between PU coating and concrete surface. The influences of the casting
conditions on the hardened concrete surface were characterized by SEM, FT-IR
and profilometry. Secondly, this study was undertaken to determine if the surface
properties of concrete could influence the adhesion of PU coating. Fracture
energies were measured by a specific 90-peel test. This method was retained
because it is appropriate to characterize the adhesion of thin films [58]. Some
publications have already showed the use of strengthened membrane or mesh
sheet that were incorporated into the bulk of soft material to characterize [9].
Concerning our system, the introduction of a polymer membrane into the bulk of
the coating was necessary to strengthen the system and measure a reproducible
adhesion of the PU coating. After the peel tests, the FT-IR analyses of the
debonded faces were undertaken to detect the residues of concrete or coating and
determine the loci of failure. FT-IR spectroscopy allows detecting organic
compounds of coatings [10, 11] and several components of concrete [12].

2 Material and methods


2.1 Material
2.1.1 Substrates made of hardened concrete
A high-performance concrete was prepared by mixing 31% of white Portland
cement (CEM I 52.5 PMES from Lafarge), 9% of limestone filler (DURCAL 1),
7% of silica fumes (MST), 43.5% of sand (BE01) and 1.5% of admixture. A
water to cement ratio (W/C) of 0.26 was used. The samples were prepared by
pouring the fresh concrete mixture into horizontal and rectangular formwork
(15x12x1 cm) made of PVC or POM. The concrete samples were removed from
their formworks after 18 hours and were stored during 28 days under ambient
conditions (25C; 50% relative humidity) to complete their hydration. Some
concrete samples were then sandblasted after demoulding (by using a powder of
corindon) to increase their roughness. The sandblasted samples were cleaned by
air flow to remove the dust before the deposition of coating.
2.1.2 Coating and conditions of deposition
The PU coating was composed of 50% of isocyanates diluted into 45% of
solvent (butyl acetate). A catalyst (dibutyltain laurate, DBTL) was added into
the mix to initiate the reaction with water (present in concrete or in atmosphere).
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The isocyanates units reacted with water to produce a polyurea-based film [13].
The coatings were sprayed (120 g/m) with air pressure of 3 atmospheres on the
concrete surface. The drying period was about 3 days under ambient conditions
(25C, 50% relative humidity) before peeling.
2.2 Methods of characterization
2.2.1 Scanning electron microscopy (SEM)
Samples were characterized by using a high-resolution field-effect gun digital
scanning electron microscope (SEM FEG Quanta 400 from FEI Company; using
an accelerating voltage of 15 keV and a current intensity of 1 nA). Images of the
cross-sections were obtained after being polished.
2.2.2 Profilometry
The roughness of concrete samples was measured with a Surftest SJ-201 M
mechanical profilometer (Mitutoyo) in order to calculate the arithmetic mean of
the profile deviations from the mean line (Ra). The Ra value was obtained by
compiling the arithmetic mean of 5 profiles of 12.5 mm.
2.2.3 Fourier transform-infrared spectroscopy (FT-IR)
The FT-IR spectrometer Nicolet iS10 (Thermo Fisher Scientific Inc.) was
equipped with a deuterated triglycine sulfate (DTGS) detector and controlled by
OMNIC software. The Attenuated Total Reflexion (ATR) mode was mainly used
in this study. FT-IR (in ATR mode) characterized the sample over a thickness of
a few m. The sampling area analyzed was approximately 1 mm. The crystal
used was made of diamond and 16 scans were routinely recorded over the range
4,000-650 cm-1 with a spectral resolution of 4 cm-1. The background was
collected at ambient atmosphere before analyzing each sample. Spectra were
corrected with a linear baseline. No specific preparations of the samples of
concrete and coating were performed before FT-IR analyses: they were studied
just after demoulding or after debonding.
2.2.4 Specific peel tests of concrete/coating system
Peel test allows measuring the debonding force (F). According to the peel angle
() and the width of the adhesive coating (w), the fracture energy (G) could be
calculated according to [14]:
F
G
w

1 cos

In the specific case of 90 peel angle, G is equal to the peeling force (F)
divided by the width (w) of the adhesive coating. The coating was strengthened
by inserting a membrane. The membrane was firstly cut in polyamide 6.6 tissues
(Nytex from Dutscher SAS) and deposited on each concrete samples. The
coating was directly sprayed on this membrane in order to avoid any air bubble
at the interface. Finally, the edges of the membrane were cut to avoid any shear
during the debonding. The membrane was flexible but non-stretched under the

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30 Materials Characterisation V
solicitations that occurred during the peel test. The dimensions of each
membrane were 200 mm long, 20 mm wide, 120 m thick, with an open porosity
of 50% and a mesh opening of 150 m. We observed by SEM (Figure 1) a crosssection of the concrete/coating interface in order to describe the system. No
mechanical step was used to initiate the crack at the interface. All the 90-peel
tests were performed with a 1000 N sensor, equipped with a specific mobile
table (as detailed by Figure 2). All the peel tests were performed under ambient
conditions (25C, 50% relative humidity) and by using a constant speed of peel
(0.2 mm/s).
Strengthened membrane

PU coating
(130 m thickness)

Concrete surface

Figure 1:

Figure 2:

SEM image of a cross-section of the concrete/coating system.

Schema and image of the experimental test of peeling.

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3 Results
3.1 Analyses of the surfaces of reference materials
3.1.1 Concrete surfaces according to the nature of the mould
Table 1 details the IR bands of concrete (demoulded with PVC). Portlandite (at
3640 cm-1) and C-S-H*/silica (large band at 1078 cm-1) were well detected.
Moreover, three strong bands were also assigned to the presence of CaCO3. Their
detection confirmed previous studies [12]. Detection of CaCO3 could be due to
the carbonation process but also due to the use of limestone filler in concrete
mix. As presented by Table 1, concrete demoulded with POM (spectrum not
shown) underlines distinct IR bands at 935 and 900 cm-1 that were assigned to
alite [15] (a component of the cement before hydration). This FT-IR spectrum
showed also peaks at 1092 and 800 cm-1, assigned to Si-O bonds from silica
fumes [12]. These silica fumes and alite are usually present into the bulk of
concrete sample. Moreover, no IR band of the portlandite (Ca(OH)2) was
detected.
Table 1:

Assignment of FT-IR bands recorded on reference materials.


FT-IR bands
(cm-1)

Concrete
(PVC mould)

O-H; Ca(OH)2

3640

C=O; CaCO3

1410; 872; 710

Si-O; silicates, CSH

1080-970

Assignment

Concrete
(POM mould)

PU
coating

Si-O; C3S

935; 900

Si-O; silica

797; 777

CH2/CH3; methyl units

2850; 2950; 1450

N-H; urea

3335

NCO; isocyanates

2270

C=O; urea

1690

The concrete samples were also studied by SEM. Concrete demoulded with
POM (Figures 3a and 3b) appears to be rougher than concrete demoulded with
PVC (Figures 3c and 3d). The flat topography observed after using PVC mould
contrasted with the heterogeneous surface obtained after using a POM mould.
These observations confirmed the measurements obtained by profilometry
(Table 2): the Ra values of concrete could vary according to the demoulding
process. Indeed, the results obtained by SEM suggest that a tearing of the
extreme surface of concrete could happen during the removing of the POM
mould. This hypothesis could explain why silica fumes were easily observed by
SEM (Figure 3b) and why alite was detected by FT-IR spectroscopy (Table 1).

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32 Materials Characterisation V
(a)

(b)

Silica fumes

(d)

(c)

Figure 3:

SEM images recorded on concrete samples: (a, b) if POM mould;


(c, d) if PVC mould.

Table 2:

Roughness of concrete according to the demoulding and posttreatment.

Ra roughness (m)

Concrete (POM mould)

Reference

0.7 m +/- 0.3

Concrete (PVC mould)


0.5 m +/- 0.3

After sandblasting

12.2 m +/- 0.4

12.1 m +/- 0.5

3.1.2 Concrete surfaces after sandblasting


Table 2 summarizes the roughness of sandblasted concrete, compared to the one
before demoulding. The initial roughness of 0.5-0.7 m range (depending on the
nature of mould used) increased to a higher Ra values of 12 m after
sandblasting (whatever the nature of the mould used). SEM images of the
sandblasted concrete, presented in Figure 4, could be compared to the ones of the
reference concrete samples (Figure 3). The sandblasted surface was rougher than
after demoulding. Silica fumes were also detected after sandblasting.
Figure 5 compares FT-IR spectra recorded on concrete (PVC mould) samples
before and after sandblasting. The intensity of the bands assigned to the CaCO3
compounds (at 1410, 870 and 710 cm-1) decreased after sandblasting while the
intensity of peaks of alite (at 930-900 cm-1) and silica (at 1100 cm-1) increased.
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Materials Characterisation V

33

Silica fumes

Figure 4:

SEM images of concrete (PVC mould) samples after sandblasting.

CaCO3

(b)

(a)
Silica

Figure 5:

Alite

FT-IR spectra of concrete samples (PVC mould): (a) before


sandblasting; (b) after sandblasting.

3.1.3 PU coating with membrane


FT-IR spectroscopy is known to determine the degree of crosslinking of the
isocyanates because a band at 2270 cm-1 characterizes presence of isocyanates
units [16, 17]. In this study, no results of adhesion were linked to the degree of
crosslinking of the coating. However, Table 1 underlines other IR bands assigned
to the presence of urea units (at 3335 and 1690 cm-1). These bands were used to
detect the residues of PU coating after peeling. The membrane made of
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34 Materials Characterisation V
polyamide 6.6. was also analyzed by FT-IR in order to assign the reference peaks
(amide units at 3300, 3070, 1630 and 1530 cm-1). However, these IR bands of the
polyamide were never detected at the interface after debonding.
3.2 Results of peel tests and FT-IR analyses of the interface after debonding
3.2.1 Influence of the mould used to cast the concrete
Figure 6 compares the peel curves obtained during the debonding of PU coating
from concrete samples. The adhesion of the coating varied according to the
nature of the casting mould.
1400

1200

(a) Concrete
(POM mould)

G (N/m)

1000

800

600

(b) Concrete
(PVC mould)

400

200

0
0

10

20

30

40

50

60

70

80

Length of debonding (mm)

Figure 6:

Peel curves of coating recorded on concrete samples: (a, in blue) if


POM mould; (b, in red) if PVC mould.

As described by Table 3, the fracture energy measured during the peel of the
PU coating from concrete (POM mould) is higher (1000 N/m +/- 150) than the
one measured during the peel from concrete (PVC mould): 400 N/m +/-50.
Figure 7a presents the FT-IR spectrum recorded on concrete (POM mould) side
after peeling: almost all the IR bands were assigned to the residues of coating
that covered the entire surface. These results confirm that the high fracture
energy was linked to a debonding into the bulk of the coating. It could also be
deduced that the adhesion between concrete and coating was better than 1000
N/m. On the contrary, Figure 7b shows FT-IR spectrum of concrete (PVC
mould) side after peeling: compounds of concrete (such as CaCO3, silica and
portlandite) were mainly detected. Concerning the internal side of coating after
peeling from concrete (PVC mould) sample, all the IR bands (spectrum not
shown) were assigned to the own components of the coating. No FT-IR bands
could be assigned to concrete residues.

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Materials Characterisation V

Table 3:

Sample

35

Results obtained by peel tests and by FTIR analyses of the


interface.
Post-treatment of concrete
before coating

Fracture
energy (N/m)

Failure localization deduced


from FTIR analyses

1000 +/- 150

Inside the PU coating

Sandblasting

1200 +/- 100

Inside the PU coating

400 +/- 50

At concrete/PU interface

Sandblasting

1200 +/- 100

Inside the PU coating

Concrete/POM

Concrete/PVC

(a) Concrete side (POM mould) after debonding

(b) Concrete side (PVC mould) after debonding

Figure 7:

FTIR spectra of concrete sides after peeling: (a) if POM mould; (b)
if PVC mould.

These data allow concluding that the debonding occurred at the interface
between concrete and coating. The fracture energies and FT-IR analyses of the
locus of failure could be correlated to the SEM observations of concrete surface
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36 Materials Characterisation V
before the deposition of the coating. Figure 3 had highlighted that the surface of
concrete demoulded with POM was more heterogeneous than concrete
demoulded with PVC, which was smoother. We can deduce that the liquid
coating (before crosslinking) strongly diffused and anchored into the
heterogeneous concrete surface, demoulded with POM. On the contrary, the
smooth and close concrete demoulded with PVC did not allow a high mechanical
anchorage of the coating.
3.2.2 Influence of the sandblasting of concrete surface
The peels tests undertaken on the sandblasted concrete (PVC mould) highlighted
high fracture energies (about 1200 N/m) while the peel undertaken on reference
concrete (PVC mould) samples induced a low level of adhesion of the PU
coating (350-400 N/m), as described in Figure 8a. Concerning concrete
demoulded with POM, the fracture energies (presented in Figure 8b) did not
1600

(a)

1400

Sandblasted concrete
(PVC mould)

1200

G (N/m)

1000
800
600

Not-sandblasted concrete
(PVC mould)

400
200
0
0

10

20

30

40

50

60

70

80

Lenght of debonding (mm)

1600

(b)
1400

Sandblasted concrete
(POM mould)

1200

G (N/m)

1000

Not-sandblasted concrete
(POM mould)

800
600
400
200
0
0

10

20

30

40

50

60

70

80

Length of debonding (mm)

Figure 8:

Peel curves of the coating recorded on concrete with or without


sandblasting: (a) if PVC mould; (b) if POM mould.

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Materials Characterisation V

37

evolve: they were as high after sandblasting as after demoulding. Thanks to these
results, we can conclude that a sandblasting of concrete demoulded with PVC
could be interesting to enhance the adhesion of PU coating. As described by
SEM images (Figure 4) and values of roughness (Table 2), the open porosity and
the roughness of concrete demoulded with PVC were higher after the
sandblasting (Figure 4c) than after demoulding (Figure 3c). On the contrary, the
sandblasting was less helpful with concrete demoulded with POM because the
open porosity was already present after demoulding. FT-IR analyses of concrete
sides were performed after peeling but only residues of coating were detected on
these concrete sides (whatever the nature of mould used). The debonding
occurred inside the layer of the PU coating if the substrate had been sandblasted
before the deposition of the coating.

4 Conclusion
A specific methodology of 90-peel test was used to measure the fracture energy
between concrete and PU coating. By introducing a porous and thin membrane to
strengthen the layer of coating, measurements were reproducible and allowed
comparing the fracture energies with the FT-IR analyses of the loci of failure
recorded after debonding. These results were correlated to the surface properties
of the reference concrete surface after demoulding (topography, composition,
roughness) that were characterized by several methods. The influence of the
nature of mould was significant. Some moulds, such as POM, could induce a
micro-tearing of the extreme surface of concrete during the demoulding. This
phenomenon increased the roughness (and the open porosity) of concrete and
improved the anchorage of the liquid coating (before its crosslinking). On the
contrary, the smooth and flat concrete surface induced after using a PVC mould
did not allow a good adhesion of PU coating. The influence of the mechanical
anchorage was confirmed by the high fracture energies measured on the
sandblasted samples of concrete. In future, analyses of the surface porosity and
sorptivity will be performed to confirm these results.

References
[1] Dubosc, A., Escadeillas, G. & Blanc, P.J., Characterization of biolical
stains on external concrete walls and influence of concrete ad underlying
material. Cement and Concrete Research, 31, pp. 1613-1617, 2001.
[2] Manoudis, P.N., Karapanagiotis, I., Tsakalof, A., Zuburtikutis,
I., Kolinkeova, B. & Panayiotou, C., Surface properties of
superhydrophobic coatings for stone protection. Journal of Nano Research,
8, pp. 23-33, 2009.
[3] Chattopadhyay, D.K. & Raju, K.V.S.N., Structural engineering of
polyurethane coatings for high performance applications. Progress in
Polymer Science, 32, pp. 352-418, 2007.

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38 Materials Characterisation V
[4] Carmona-Quiroga, P.M., Martnez-Ramrez, S., Sobrados, I. & BlancoVarela, M.T., Interaction between two anti-graffiti treatments and cement
mortar (paste). Cement and Concrete Research, 40, pp. 723-740, 2010.
[5] Barquins, M. & Ciccotti, M., On the kinetics of peeling of an adhesive tape
under a constant imposed load. International Journal Adhesion and
Adhesives, 17, pp. 65-68, 1997.
[6] Horgnies, M., Darque-Ceretti, E. & Combarieu, R., Adhesion of pressure
sensitive adhesives to automotive coatings: Influence of topcoat
composition. Journal of Adhesion Science and Technology, 18, pp. 10471061, 2004.
[7] Johnson, K.L., Kendall, K. & Roberts, A.D., Surface Energy and the
contact of elastic solids. Proceedings of Royal Society of London, 324, pp.
301-313, 1971.
[8] Kinloch, A.J., Adhesion and adhesives: science and technology. Chapman
and Hall, London, New York, pp. 66-73, 1987.
[9] Giannis, S., Adams, R.D., Clark, L.J. & Taylor, M.A., The use of a
modified peel specimen to assess the peel resistance of aircraft fuel tank
sealants. International Journal of Adhesion and Adhesives, 28, pp. 158-175,
2008.
[10] Almeida, E., Balmayore, M. & Santos, T., Some relevant aspects of the use
of FT-IR associated techniques in the study of surfaces and coatings.
Progress in Organic Coatings, 44, pp. 233-242, 2002.
[11] Poliskie, M. & Clevenger, J.O., Fourier Transform Infrared (FT-IR)
spectroscopy for coating characterization and failure analysis. Organic
Finishing, pp. 44-47, 2008.
[12] Chollet, M., Horgnies, M., Analyses of the surfaces of concrete by Raman
and FT-IR spectroscopies: comparative study of hardened samples after
demoulding and after organic post-treatment. Surface and Interface
Analysis, In press.
[13] Agrawal, R.K. & Drzal, L.T., Adhesion mechanisms of polyurethanes to
glass surfaces. Part I. Structure property relationships in polyurethanes and
their effects on adhesion to glass. Journal of Adhesion, 54, pp. 79-102,
1995.
[14] Kendall, K., Thin-film peeling the elastic term. Journal of Physics D:
Applied Physics, 8, pp. 1449-1452, 1975.
[15] Frost, R.L., Cejka, J. & Weier, M.L., Molecular structure of the uranyl
silicates a Raman spectroscopic study. Journal of Raman spectroscopy,
37, pp. 538-551, 2005.
[16] Daniel-da-Silva, A.L., Bordado, J.C.M. & Martin-Martinez, J.M., Moisture
curing kinetics of isocyanate ended urethane quasi-prepolymers monitored
by IR spectroscopy and DSC. Journal of Applied Polymer Science, 107, pp.
700-709, 2007.
[17] Agrawal, K. & Drzal, L., Adhesion mechanisms of polyurethanes to glass
surfaces. Journal of Adhesion Sciences Technology, 9, pp. 1381-1400,
1995.

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Section 2
Nano-materials

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Materials Characterisation V

41

HRTEM techniques applied to nanocrystal


modeling: towards an atom-by-atom
description
D. G. Stroppa1,2, L. A. Montoro1, E. R. Leite3 & A. J. Ramirez1,2*
1

Brazilian Synchrotron Light Laboratory, Brazil


Mechanical Engineering School, University of Campinas, Brazil
3
Department of Chemistry, Federal University of So Carlos, Brazil
2

Abstract
The development of technologies based on nanostructures presents a wide range
of challenges for materials scientists and engineers, including the attainment of
well-controlled synthesis procedures, the improvement of characterization
techniques down to the atomic scale resolution, and the conception and
validation of reliable models that can describe materials properties as functions
of their morphology and fabrication process. A relevant topic in this scenario is
the correlation among the spatial distribution of chemical elements, the surface
energy configuration, the growth mechanism, and the resultant nanocrystal 3D
morphology.
This work presents an overview on the use of advanced HRTEM techniques
for the quantitative analysis of nanocrystals and how these results can be used to
implement nanocrystals models, which can analytically describe the material
features on an atomic level. The presented findings show the combined use of
experimental data and theoretical tools, such as image simulation and ab initio
surface energy calculations, for the advanced quantitative characterization of
nanocrystalline systems.
The combination of experimental and theoretical efforts on HRTEM
characterization represents a powerful tool for the nanocrystal 3D morphology
elucidation with atomic resolution and the chemical/structural properties
assessment in a quantitative way. Thereby, it is presented as the stepping stone
towards the development of novel approaches to describe nanostructured
systems.
Keywords: HRTEM, nanocrystals modeling, quantitative analysis.
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42 Materials Characterisation V

1 Introduction
Nanotechnology has been considered one of the most promising branches on the
scientific development since the 60s [1] and its contributions to various fields
are notorious nowadays. The nano suffix and its effects became an intrinsic
subject of materials science and technology on the last few years as the unique
properties from nanometer scale are becoming increasingly relevant in those
fields.
The traditional materials engineering perspective [2], depicted in Figure 1,
can also be applied for the analysis of nanostructured systems. This approach
considers that the design of materials aiming an optimum performance requires
the complete understanding of the correlation among the processing routes
parameters, the materials structure and the resultant properties. However,
regarding nanostructured systems, this correlation may be stated as the
interrelationship among the synthesis parameters, the atomic scale morphology
and the energy configuration [3]. As the surface area to volume ratio is enhanced
for such systems, unique properties related to the surface energy distribution
become relevant. These properties are the source for the unique performance of
nanomaterials [4].

Figure 1:

Engineering approach for describing and correlating materials


features.

Materials characterization plays a crucial role on the development of reliable


models for the description and the design of nanostructured materials with
specific features for countless technological areas. Apart from the specific
questions that different characterization techniques may answer, there are three
general issues that can be highlighted as the most relevant questions for the
nanostructured materials modeling and design.
The first one is related to the morphology characterization at the atomic scale.
As mentioned before, it is vital to assess the nanomaterials structure with high
resolution in order to evaluate its correlation with the system properties. The
ultimate goal in this sense is the atom-by-atom description of nanocrystals,
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Materials Characterisation V

43

which would be specially required for the determination of atomic species


segregation on alloyed/doped materials [5] and the high resolution strain state
analysis of nanostructures [6].
The second issue is related to the nanocrystals surface structure and its
dependency on the synthesis environment and chemical species. This aspect is
intrinsically correlated to the nanocrystals morphology and, consequently, to the
material surface energy distribution and properties [7].
The third relevant point is the interrelation between the nanocrystals and the
system growth behavior [8]. These aspects represent crucial issues for the
understanding and optimization of synthesis methodology as they are closely
related to the nanostructured system stability and long term reliability [9].
As describing the properties and behavior of each nanocrystal in an actual
nanostructured system represents an overwhelming many-bodies problem,
simplified models are needed for the engineering of nanomaterials in a reliable
manner. Nanocrystal modeling [10] is a wide approach where nanostructured
systems components are described as building blocks with specific morphology,
energy distribution, and interaction mechanisms. In these terms, the development
of accurate models may be a fundamental tool for nanocrystals and mesocrystals
shapes prediction, design and control of growth processes, and the resulting
properties tuning of an unlimited number of systems.
The development of reliable modeling methodologies represents a hard task
for materials scientists and engineers due to involved challenges, especially
when quantitative high resolution characterization analyses are required. Even
though advanced characterization techniques based on electron microscopy,
scanning probe microscopy and synchrotron radiation are feasible and
complimentary in this scenario, limitations [11] associated to each one of them
prevent their isolated use a for reliable analysis. The most relevant limitations of
high resolution techniques are summarized on Table 1.
Table 1:

Most relevant limitations from high resolution characterization


tools.

ISSUE
Sample Preparation
Sample Stability
Energy Resolution
Signal to Noise Ratio
Sampling
Averaging
Data Analysis

EFFECT
modification on the sample original features
characteristics changes during analysis
spectroscopic signature may have overlaps
poor detection system sensitivity
lack of statistical representativeness
lack of features from individual particles
deconvolution, modeling and fitting

Although continuous improvements on the characterization instrumentation


and methodologies enhance the individual techniques performance, the
combined use different available experimental techniques and theoretical
approaches are widely used to overcome the inherent limitations of the
quantitative analysis of nanosized systems.
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44 Materials Characterisation V
Transmission Electron Microscopy (TEM) based techniques stand out among
other characterization techniques for nanostructured systems due to the
possibility of a comprehensive and versatile approach including high resolution
imaging, diffraction and spectroscopy. This multipurpose characteristic allied
with simulation procedures provides complementary information that can be
used to improve the analysis precision.
Recent developments on the TEM instrumentation and analysis methods
allowed outstanding advances on nanoscience and nanotechnology [12]. The
spherical aberration (Cs) correction [13] can be considered among the most
influential improvements on both high resolution TEM (HRTEM) and high
resolution scanning TEM (HRSTEM) due to a number of factors. For HRTEM,
the Cs-correction of the objective lens resulted in the drastic improvement on
achievable spatial resolution, the possibility of larger gaps in the pole piece for in
situ experiments, and new imaging modes [14] due to fine tuning of the
aberration coefficients. For HRSTEM, the Cs-correction of the condenser lens
leads to an improvement on the achievable spatial resolution due to the probe
size reduction and the effective beam current increase.
In addition to the instrumental TEM improvements, the development of more
accurate models to describe the image formation and to support the TEM image
simulation [15] provides a more reliable interpretation of experimental data.
This work presents an overview on the HRTEM techniques state of art with
several examples which indicate the development of such characterization tools
towards the quantitative high resolution analysis of nanocrystalline materials.

2 HRTEM and HRTEM image simulation


HRTEM image formation is based on the incident electron beam scattering by a
thin sample. The technique is especially relevant for very thin crystalline
samples, where the interaction of the several diffracted beams forms an
interference patterns. As the diffracted components correspond to particular
oriented periodic spacings on the sample, their interference may appear as a 2D
periodic image which cannot be directly interpreted. The direct interpretation
unfeasibility is mainly related to the HRTEM interference pattern dependency
with the sample thickness and with the microscope configuration, especially the
defocus value. However, the use of HRTEM image simulation can provide
information about the sample crystalline arrangement.
HRTEM image simulation is a crucial step in HRTEM characterization,
which supports the atomic structure analysis. Multislice method [16] is the most
widely used image simulation procedure and consists in the electrons wave
function calculation after the electron beam interaction with the sample projected
potential. Imaging distortions due to the lens aberrations, microscope instabilities
and detection system defects [17] may be included in order to better reproduce
the experimental imaging condition.
The HRTEM imaging and image simulation combination has provided
numerous examples of successful materials characterization. Remarkable
examples can be noticed on the determination and refinement of crystalline
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Materials Characterisation V

45

structures [18] and the quantitative evaluation of the chemical composition


profile along the thin films interface [19].
Figure 2 illustrates the combination of HRTEM imaging and image
simulation on the evaluation of an anomalous anisotropic growth mechanism for
SnO2 nanocrystals [20]. The used approach provided an unambiguous
characterization of the growth mechanism and its preferential direction, which
would not be feasible from direct imaging only.

Figure 2:

(a) SnO2 nanocrystal HRTEM image with an indexed FFT inset and
a HRTEM multislice simulation (red square). (b) oriented
attachment along the [110] is identified as the main growth
mechanism. [From ref. [20], copyright 2011 by RSC Publishing,
reprinted with permission of authors.]

In addition, the accurate determination of nanocrystals 3D morphology by


HRTEM simulation of nanocrystals [21] can be used to indirectly extract
quantitative dopant segregation information [22] from systems where
conventional analytical techniques are impracticable due to several experimental
restrictions. Figure 3 depicts the 3D morphological modeling for Sb:SnO2
nanocrystals with different dopant contents. The nanocrystals models were
compared to the Wulff [23] constructions based on ab initio surface energy
calculations, providing the dopant atoms segregation for individual particles and
its dependency with the doping level [24].
The presented examples depict the synergism between the HRTEM imaging
and theoretical methods such as HRTEM image simulation and ab initio surface
energy calculations. Therefore, this combination presents a remarkable potential
as a tool for unveiling important nanocrystalline systems features, such as 3D
morphology, dopant segregation, surface energy distribution, and growth
mechanisms.

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46 Materials Characterisation V

Figure 3:

(a), (e) Trimetric and (b), (f) [111] zone-axis oriented views for the
Sb-doped nanocrystals geometric model. (c), (g) Original HRTEM
images and (d), (h) superimpositions with the simulated HRTEM
images. [Adapted from ref. [22], copyright 2009 by ACS
Publications, reprinted with permission of authors.]

3 Focal series reconstruction and geometric phase analysis


Although the HRTEM image simulation can support accurate nanocrystals 3D
morphology analyses, it is not always feasible to use such procedure to precisely
evaluate the position of individual atoms or atomic columns in crystalline
structures. To extract information which is directly related to the atomic positions,
such as strain/stress state, a refinement on the HRTEM analysis is needed.
Focal Series Reconstruction (FSR) [25] is a proposed calculation which is
applied for the electron wavefunction restoration on the HRTEM imaging
process and allows obtaining the sample projected potential without the
interference of the microscope optical aberrations. The FSR implementation is
based on the acquisition of a set of images under different objective lens defocus
conditions, which is subsequently submitted to a restoration procedure that
estimates the contrast transfer function (CTF) and the aberration coefficients
implicated on the imaging process.
A number of successful uses of FSR aiming a straightforward image
interpretation [26], the correction of residual aberration [27], and the
improvement of the HRTEM technique spatial resolution [28] have been already
described in the literature. An example which illustrates the image improvement
when FSR method is applied to structural analysis is depicted on Figure 4. These
images show the comparison between an original HRTEM image and a phase
image of the reconstructed wavefunction [29].
Geometric Phase Analysis (GPA) [30] is a methodology for measuring and
mapping structural displacement fields on HRTEM images using a reference
lattice. Its application to HRTEM image analysis allows the local lattice
distortion evaluation, which can be directly related to the local strain state. This
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Materials Characterisation V

47

method has been effectively employed to study strain fields in semiconductors


and metals [31].
The GPA implementation is based on the reciprocal space evaluation of a
HRTEM image with respect to a reference undistorted lattice image, either
obtained from a different region in the analyzed sample or from an image
simulation procedure. As a spatial frequency spread around the characteristic
lattice parameters frequencies is existent on strained samples, the determination
of lattice distortions can be performed by the comparison with a reference image.
The distorted components can be extracted on the reciprocal space and further
translated to real space components through an inverse Fourier transform. Such
analysis can be performed for two non-collinear spatial frequencies, resulting in
a projected 2D distortion description of the sample which can be related to its 2D
strain/stress state.

Figure 4:

(a) Example of an original HRTEM image and (b) the output from
a FSR restoration from a CoSi2 sample. The insets exhibit a higher
magnification detail with the crystal structure superimposition.
[Adapted from ref. [29], reprinted with permission of authors.]

The GPA application is reported on the literature as an efficient tool to


calculate strain maps on microelectronic components [32] and for the strain state
analysis on individual nanocrystals [33]. A typical output from a GPA analysis is
the distortion map from the analyzed HRTEM image, as exemplified on Figure
5, which includes the perpendicular, parallel and rotational strain components.
An example of the combined user of FSR and GPA is presented on Figure 6
[34]. Cross-section HRTEM images of epitaxially grown Si1-xGex:Si(001)
alloyed islands were used to characterize in a self-consistent way the strain
configuration and the local chemical composition with high spatial resolution.
By the combination of projected 2D chemical composition mapping from two
different cross-sectioned zone-axis views, [100] and [110], it was possible to
infer the chemical composition in a three-dimensional fashion [35].

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48 Materials Characterisation V

Figure 5:

(a) Original Cs-corrected HRTEM image and (b) distortion


mapping from a single dislocation on a CeO2 sample.

Figure 6:

(a) FSR reconstruction from a Si-Ge island including a higher


magnification detail on the inset. (b) A simplified 3D chemical
reconstruction was obtained after the strain chemical mapping of
several Si-Ge islands at different zone-axis. An example from a
single island: (c) chemical composition map, (d) parallel and (e)
perpendicular strain projections. [Adapted from refs. [34] and [35],
copyright 2009 by ACS Publications, reprinted with permission
of authors.]

The successful application of this technique to quantify the elastic behavior of


the Si-Ge:Si(001) system shows that this methodology arises as a remarkable
tool for accurate chemical and elastic state evaluation, which can be applied to
several strained alloyed nanostructures, such as epitaxial islands, nanowires,
nanocrystals, and thin films.

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Materials Characterisation V

49

4 A novel approach for HRTEM imaging


The improvement of HRTEM characterization depends on the comprehensive
understanding of the underlying image formation theory. An important imaging
condition representation is given by the Contrast Transfer Function (CTF), which
represents how the spatial frequencies are transmitted through microscope
imaging system.
Since the 40s, microscopists have been trying to improve the CTF
characteristics by tuning the instruments parameters during the experiments or
by the posterior treatment of the images. The main goal in this sense is to extend
information transfer for high spatial frequencies. The most remarkable
improvements were achieved by using induced defocus values on the objective
lens in order to compensate its inherent positive spherical aberration coefficient
[36]. However, a ground-breaking evolution happened on HRTEM with the Cscorrection possibilities.
At a first glance, the use of Cs-correction adds an additional degree of
freedom to the microscope tuning, allowing the CTF direct improvement for
high spatial frequencies and improving the microscope information limit. A
comparison between the HRTEM images from the same sample obtained by
conventional and Cs-corrected microscopes, which is presented on Figure 7,
clearly shows the image enhancement provided by the aberration corrector
hardware.

Figure 7:

Raw HRTEM images from the same CeO2 nanocrystal from a (a)
standard TEM microscope (1.25 information limit) and from a
(b) Cs-corrected microscope (0.8 information limit).

A detailed investigation [37] of the electron scattering on the dynamical


regime pointed out that non-linear contributions would enable the achievement
of enhanced contrast transfer for low-Z elements by the use of negative Cs
values. The Negative Cs Imaging (NCSI) [14] aims the contrast maximization at
high frequencies by the microscope parameters optimization, including defocus
and Cs adjustments. The NCSI application allowed some unique measurements
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50 Materials Characterisation V
including the high resolution assessment of light elements atomic columns
information, such as occupancy next to crystalline defects [38] and sub-angstrom
displacement in magnetic domain walls [39].
Examples of NCSI HRTEM characterization for CeO2 sintered and
nanocrystalline samples are depicted on Figure 8. Although the contrast for
Oxygen columns is observed in both images, the direct analysis of a bulk-like
sample HRTEM image (Figure 8a) is unfeasible due to a combination of factors.
As the accurate thickness estimation is not achievable by HRTEM image
simulation for this specific combination of crystalline system and imaging
conditions, the intensity distribution cannot be directly associated to the Oxygen
columns scattering. A solution for this issue is the sample projected potential
assessment by the FSR application on NCSI HRTEM images (Figure 8b).

Figure 8:

(a) NCSI HRTEM image from a CeO2 bulk-like sample on the


[100] ZA and (b) FSR from NCSI HRTEM images from a CeO2
nanocrystal on the same ZA orientation including a unit cell
superimposition.

5 Concluding remarks
State of art HRTEM techniques indicate that their use in conjunction with
theoretical procedures for HRTEM image simulation and data analysis represents
a vital tool for the quantitative evaluation of nanostructured systems. The
depicted examples illustrate how this technique can simplify, or even present
completely novel approaches, a number of materials characterization challenges
where a quantitative high resolution assessment is required.
The current development of HRTEM instrumentation and related
methodologies indicates that its importance on materials characterization will
grow on this decade, especially due to the novel possibilities achieved by
aberration correction implementation and by on-growing combined use with
HRSTEM imaging and spectroscopy techniques.

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Acknowledgements
The authors acknowledge the financial support of the Brazilian research funding
agencies FAPESP and FINEP; the German research funding agency DAAD. The
authors would also like to thank the Ernst Ruska Centre staff at the
Forschungszentrum Jlich and the QFA staff at the Universitat Jaume I for the
fruitful discussions and scientific support.

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Materials Characterisation V

55

Ca(OH)2 nanoparticle characterization:


microscopic investigation of their application
on natural stones
V. Daniele & G. Taglieri
Department of Chemistry, Chemical Engineering and Materials,
University of LAquila, Italy

Abstract
Owing to conversion of lime into calcium carbonate, lime is usually adopted for
conservative surface treatments. However, some critical aspects concerning the
treatments reduced penetration depth, the binder concentration and the
incomplete lime carbonation process still represent undesired limits and
hindrances. In order to improve lime treatments, Ca(OH)2 particles with
nanometric dimensions (nanolime) have recently been introduced in Cultural
Heritage conservation (frescoes, stuccoes, ..). The aim of the present work is to
characterize Ca(OH)2 nanoparticles synthesized by a chemical precipitation
process starting from two base supersaturated aqueous solutions of calcium
chloride and sodium hydroxide. After several washes, necessary to remove the
sodium chloride, the aqueous medium is partially substituted by 2-propanol to
improve the suspension stability; an alcoholic nanolime suspension is obtained,
characterised by a given concentration and a residual water content. In order to
identify the structure of the formed phases and the particles reactivity, the
obtained nanolime is characterised by X-ray diffraction (XRD) and profile
analysis; scanning and transmission electron microscopy (SEM-TEM) are
performed too. The results show hexagonally plated and regularly shaped
particles with side dimensions equal to or less than 300nm; moreover particles
have pure crystalline features and a high reactivity in terms of the carbonation
process. Finally, the Ca(OH)2 nanoparticles are applied on some natural
lithotypes; SEM analyses are performed to evaluate penetration depth and grain
adhesion of the nanolime treatments itself. From SEM micrographs a partial
filling of the lithotypes pores, located at a distance from the surface of more than
200m, is observed.
Keywords: calcium hydroxide, consolidation, lime, nanoparticles, protection.
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56 Materials Characterisation V

1 Introduction
Thanks to conversion of lime into calcium carbonate, lime water and milk are
usually adopted for conservative surfaces treatments. In particular, lime water
consolidation is generally obtained spraying the lime solution on the cleaned
surface. To reach a good penetration, the treatment is repeated several times until
the surface is able to absorb lime water [1]; some Authors indicate that could be
necessary to repeat the application for 30-40 times [2]. Lime milk is used on the
same basis as lime water [3]; nevertheless it involves greater amounts of lime
with the same water volume, reducing the water percentage brought to the stone.
However, some critical aspects concerning the treatments reduced penetration
depth, the binder concentration and the incomplete lime carbonation process still
represent undesired limits and hindrances. In order to improve lime treatments,
Ca(OH)2 particles with submicrometric dimensions (nanolime) are recently
introduced in Cultural Heritage conservation. Lime nanoparticles present the
following advantages in stone, mortar and plaster consolidation: the possibility to
penetrate deep into damaged zones (no limitations due to the particle size), high
reactivity and fast reactions (such as carbonation) in the treated zones, high
purity and defined composition [4]. Nanolimes are successfully employed on
mural paintings, stuccoes and frescoes [59]; refurbishments of architectonical
surfaces are considered too [1012]. Lime nanoparticles are typically produced
by a chemical precipitation process in supersaturated aqueous solutions of the
reactants (calcium chloride and sodium hydroxide). To improve nanolime
particles dispersion, the use of alcoholic solutions in place of aqueous ones is
adopted; in fact, when 2-propanol alcohol is used as a solvent, dispersions of
calcium hydroxide particles show a slower rate of agglomeration (and therefore,
slower sedimentation rates) in comparison to aqueous media. This reduces the
tendency for a white film to form on surfaces to be consolidated [13].
In this paper a nanolime suspension, characterised by a residual water content
in the precipitated phase, is synthesised. X-ray diffraction (XRD) measurements
and profile analysis are performed to characterise the nanolime samples and to
evaluate the carbonation efficiency (yield). To correlate the produced nanolime
to its properties, morphological characterisation is performed by scanning and
transmission electron microscopy (SEM and TEM).
Finally, the nanolime suspension is applied by brush on cleaned stone
surfaces of natural lithotypes; in particular, the suspension is used in a diluted
form (concentration of about 1mg/ml) in order to avoid the risk of leaving a
white film on treated materials surfaces [11].
Several lithotypes, largely employed in architectonic fields, are considered:
Travertine, Pietra di Lecce, Pietra Serena and Basalto.
A local calcareous lithotype, Poggio Picenze is investigated too. SEM
analyses allow one to investigate how the nanolime penetrates inside the stone
porosity, in terms of the reached depth and the grains adhesion of nanolime
treatments itself.

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2 Experimental section
Calcium chloride dihydrate (CaCl22H2O), sodium hydroxide (NaOH) and 2propanol pro analysi products, supplied by Merck, are used without further
purification. Water is purified by a Millipore Organex system (R 18 M cm).
Two aqueous solutions of 400ml, containing 0,3mol/l of CaCl2 and 0,6mol/l
of NaOH respectively, are prepared. The NaOH solution (used as precipitator) is
added dropwise into the CaCl2 solution (speed 4ml/min, temperature of 90C).
After about 24 hours two distinct phases are observed: a limpid supernatant
solution and a white precipitated phase (NLW sample). In order to remove the
NaCl produced, several deionised water washings are performed. Subsequently,
in order to improve the suspension stability, the water content is partially
substituted by 2-propanol; the obtained suspension is characterised by a water/2propanol ratio (W/A) of 0,75 and a final concentration of about 10mg/ml (NLA
sample). SEM analyses (Philips XL30CP) are performed, depositing 0,2ml of the
suspension on the specimen; TEM investigations (Philips CM100) are carried
out dispersing 0,2 ml of the suspension in 50 ml of 2-propanol and depositing the
sample on the suitable grid.
As concerns XRD measurements, the sample is prepared maintaining the
nanolime preparation for 20 in ultrasonic bath (US) and then depositing 0,2ml
of the suspension on a silica sample holder; measures are performed on dry
sample, in laboratory conditions (T=20C, relative humidity RH=40%). Each
experimental diffraction spectrum is elaborated by a Profile Fit Software (Philips
PROFIT v.1.0) and each crystalline phase is attributed by JCPDS patterns; the
ratio between the CaCO3 peaks area and the spectrum total area is assumed as the
carbonation process efficiency (yield).
2.1 Results and discussions
TEM micrographs, obtained on NLA sample, are reported in Fig.1; in particular,
hexagonally and regularly shaped particles of side dimension ranging from 100
to about 300nm are observed. Moreover, in Fig.1b) it is possible to note that all
the particles appear overlapped in an ordered way and are so thin to be
transparent to the electron beam.

a)

b)

Figure 1:

TEM micrographs on NLA sample: a) scale bar 500nm; b) scale bar


200nm.

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58 Materials Characterisation V
In Fig. 2, SEM images on NLA sample are shown. The particles, characterised
by a prismatic features are recognizable to calcium carbonate of side dimension
less than 500nm (Fig.2a). In Fig.2b) a perfectly hexagonal and regular shaped
particle (marked as A) is observed, characterized by a side dimension less than
250nm.

a)

b)
SEM micrographs on NLA sample (scale bar 1m).

Figure 2:

XRD pattern on NLA sample shows the presence of Ca(OH)2 and CaCO3
phases (84-1276 and 85-1108 JCPDS patterns, respectively) with a
corresponding yield value of about 80% (Fig.3a). On the contrary, XRD results
obtained on NLW sample show as the corresponding yield decreases, reaching a
value of about 50% (Fig.3b). The NLA higher yield values can be attributed to
the presence of 2-propanol, that tends to disagglomerate the nanolime
particles; so, a greater specific surface of the Ca(OH)2 particles exposed to air,
can leads to a better carbonation process.
*

* CaCO3
Ca(OH)2

* CaCO3
Ca(OH)2

a)

b)
Figure 3:

XRD patterns: a) NLA sample; b) NLW sample.

3 Treatment on natural lithotypes: characterisation and


results
The considered samples, largely employed in the Italian historical architecture,
are natural calcareous stones - Travertine, Pietra di Lecce and Poggio Picenze
(the last one is a local lithotypes), a national sandstone - Pietra Serena - and an
igneous lava stone of volcanic origin - Basalto.
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The nanolime treatment is carried out by brush, in laboratory conditions


(T=20C; R.H. 50%), applying the diluted alcoholic suspension (characterised by
a concentration of 1mg/ml) on the dry and clean stones surface. In particular,
1ml of the suspension is applied on a side (5*5cm2) of the stone surface; when
the solvent is evaporated, this procedure is repeated for 100 times (giving about
100mg Ca(OH)2 for each stone). For SEM investigations, each stone sample is
broken along a plane perpendicular to the treated side and the section surface is
observed. On the following figures, SEM micrographs, referred to untreated and
treated samples section, are shown; in particular, in order to evaluate the
treatment penetration inside the stone, pores situated at different surface
distances are considered.
3.1 Travertine
In Fig. 4 SEM micrographs on untreated Travertine stone sample is reported; in
particular, a typical region, containing macropores and areas with a compact
matrix is shown. For what concerns the treated stone, it is possible to note as the
nanolime treatment covers the internal stone pore without filling it completely
(Fig.5). In particular, the treatment, well recognisable in SEM micrograph
referred to a pore at 150m from the surface (Fig.5a-b), is found also in pores
located at about 1mm from the surface itself (Fig.5c-d). This result can be
attributed to the Travertine porosimetric structure, constituted by macropores, by
which the nanolime treatment can be carried inside the stone.

a)

b)

Figure 4:

SEM micrographs on untreated Travertine stone: a) sample section


(scale bar 500m); b) zoom view on A pore (scale bar 100m).

3.2 Lecce stone


Pietra di Lecce is an organogenic marl calcareous stone, compact, generally
porous and characterised by a fine-grained structure [14]. In Fig. 6, SEM
micrographs on untreated sample are reported; it is possible to note the granular
stone structure, constituted by various size clasts and by an intergranular porosity
(Fig.6b).

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60 Materials Characterisation V
B

C
a)

b)
C

c)

d)

Figure 5:

SEM micrographs on treated Travertine stone: a) sample section


(scale bar 200m); b) zoom view on B pore localised at 150m
from the surface (scale bar 10m); c)-d) different zoom views on C
pore at about 1mm from the surface (scale bar 10m and 5m,
respectively).

a)

b)

Figure 6:

SEM micrographs on untreated Lecce stone: a) sample section


(scale bar 500m); b) zoom view on A pore (scale bar 10m).

Considering the treated sample, the treatment covers homogeneously the internal
stone pores without filling them completely (Fig.7b-c). In particular, the
treatment is also well recognisable in the pore located at 800m from the surface,
underlining the penetration depth reached from the treatment itself (Fig.7c).

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61

C
B
a)

b)
C

c)
Figure 7:

SEM micrographs on treated Lecce stone: a) sample section (scale


bar 200m); b) zoom view on B pore localised at 250m from the
surface (scale bar 10m); c) zoom view on C pore at about 800m
from the surface (scale bar 10m).

3.3 Poggio Picenze stone


Poggio Picenze lithotype, a local calcareous stone, is constituted by
heterogeneous grained material; the stone surface and its internal structure are
characterized by small-medium size pores and vacuoles (Fig.8) [14].

a)

b)

Figure 8:

SEM micrographs on untreated Poggio Picenze stone: a) sample


section (scale bar 500m); b) zoom view on A pore (scale bar
20m).

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62 Materials Characterisation V
SEM micrographs referred to treated stone, show as the nanolime treatment
tends to fill the internal cavity of the material, adhering to its grain, without
occlude the pores. In particular, the treatment, recognisable in a pore located at a
distance of 300m from the surface (Fig.9), is not found in more internal
cavities.
B

B
a)

b)
B

c)
Figure 9:

SEM micrographs on treated Poggio Picenze stone: a) sample


section (scale bar 200m); b)-c) different zoom views on B pore at
about 300m from the surface (scale bar 10 and 5m, respectively).

In particular, in Fig.9b-c) internal stone cavities, that can be related to


intergranular space, dont appear covered by the precipitated particles; this fact
can indicate that the nanolime treatment doesnt modify the porosimetric system
of the lithotype.
3.4 Pietra Serena stone
This lithotype is different from those discussed above; in fact, it is a sandstone
characterised by clay fractions. Moreover, this stone is constituted by different
grains size, ranging from medium-fine to coarse ones (Fig.10) [14].
SEM micrographs referred to the treated sample are shown in Fig.11; the
internal voids appear filled, on the walls, by precipitated particles (shaped like a
small flakes) that tend to adhere to the clasts edges, without occluding the
pores system (Fig.11b-c).

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63

a)

b)

Figure 10:

SEM micrographs on untreated Pietra Serena stone: a) sample


section (scale bar 500m); b) zoom view on A pore (scale bar
20m).
B
C

B
a)

b)
C

c)
Figure 11:

SEM micrographs on treated Pietra Serena stone: a) sample section


(scale bar 200m); b) zoom view on B pore localised at 750m
from the surface (scale bar 10m); c) zoom view on C pore at
about 450m from the surface (scale bar 10m).

3.5 Basalto stone


Basalt lithotype is an igneous rock lava of volcanic origin, typically composed
by gray-black silicates [14]. It is an hard and resistant stone characterised by
many pores and voids, of varying sizes, usually medium-large ones (Fig.12).
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64 Materials Characterisation V

a)

b)

Figure 12:

SEM micrographs on untreated Basalto stone: a) sample section


(scale bar 500m); b) zoom view on A pore (scale bar 20m).
B

C
a)

b)
B

c)

d)

Figure 13:

SEM micrographs on treated Basalto stone: a) sample section (scale


bar 200m); b)-c) different zoom views on B pore localised at
500m from the surface (scale bar 10 and 5m, respectively); d)
zoom view on C pore at about 700m from the surface (scale bar
5m).

SEM micrographs on the treated stone, show as the nanolime treatment tends
to fill the internal cavity of the material, adhering to its grain, without occluding
the porosimetric system. In particular, the treatment, is not found in pores more
internal than 700m.

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Materials Characterisation V

65

4 Conclusions
Nowadays lime nanoparticles are synthesised and employed for protection and
superficial consolidation of several artworks such as stones, plasters, frescoes,
wall paintings and paper documents.
The obtained Ca(OH)2 nanoparticles are hexagonally plated and regularly
shaped, with side dimensions generally less than 300nm, as shown by TEM
observations. From XRD analyses, the carbonation process efficiency of the
aqueous nanolime is about 50%, while the use of 2-propanol improves it
reaching a yield value of about 80%. This result underlines the 2-propanol role in
disagglomerating the particles, leaving a higher specific surface exposed to air.
SEM analyses are performed to evaluate the interaction between the nanolime
treatments and the porosimetric system of some natural lithotypes. The images
show the partial filling of the pores in all the examined lithotypes, without
occluding them. On the contrary, considering all the lithotypes, the treatment
penetration is observed at a limit distance from the surface, ranging from 300m
(Poggio Picenze stone) to about 1mm (Travertine stone).

References
[1] Vinardi, M.G., Cully, M.H., Brunetto, A., La reversibilit nel restauro.
Riflessioni, esperienze, percorsi di ricerca, In: XI National Congress
Scienza e Beni Culturali: La Pulitura delle Superfici dellArchitettura,
Bressanone, XIX, pp. 399-405, 2003.
[2] Sten, P., Lime Water Consolidation, ICCROM, 53-61, 1981.
[3] Turriziani, R., I leganti ed il calcestruzzo, Edizioni Sistema, Roma,
pp. 70-82, 1972.
[4] Pianski, J., Brmmer, K., Ziegenbalg, G., Nano-particles for stone
conservationstate of the art, characteristics and recent developments, In:
Stonecore Recent progress in the consolidation of calcareous
materials, Litomyl, Czech Republic, Aprile 2010.
[5] Baglioni, P., Cesari, C., Dei, L., Giorgi, R., Grassi, R., Lorenzetti,
M., Mauro, M., Pinzani, D., Ruffo, P., Schonhaut, G., Stucco forte
veneziano con Tecniche della Tradizione: propriet chimico-fisiche,
degrado in ambiente lagunare e conservazione mediante nanofasi cristalline
di Ca(OH)2, In: National Congress Scienza e Beni Culturali: Lo Stucco.
Cultura, Tecnologia, Conoscenza, Bressanone, XVII, pp. 289-298, 2001.
[6] Ambrosi, M., Baglioni, P., David, P.R., Dei, L., Giorgi, R., Lalli,
C., Lanterna, G., Mairani, A., Matteini, M., Rizzi, M., Schonhaut,
G., Inorganic consolidants and protectives for architectonic surfaces:
experimental tests on Santa Prisca Church Apse in Rome, In: 2nd
International Congress on Science and Technology for the safeguard of
Cultural Heritage in the Mediterranean Basin, Vol. 2, pp. 873-877, 1992.
[7] Dei, L., Salvadori, B., Arlango, E., Pietropoli, F., Scardellato, C., Gli
affreschi del XIII e XIV secolo nella Cripta di San Zeno a Verona: la
sperimentazione della nanocalce dispersa in alcol iso-propilico durante
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66 Materials Characterisation V

[8]

[9]

[10]

[11]

[12]

[13]

[14]

lintervento conservativo, In: International Congress Scienza e Beni


Culturali: Sulle pitture murali. Riflessioni, conoscenze, interventi,
Bressanone, XXI, pp. 293-302, 2005.
Dei, L., Radicati, B., Salvadori, B., Sperimentazione di un consolidante a
base di idrossido di calcio nanofasico sugli affreschi della Cappella del
Podest al Museo del Bargello di Firenze: aspetti chimico-fisici e prove di
colore, In: International Congress Scienza e Beni Culturali: Sulle pitture
murali. Riflessioni, conoscenze, interventi, Bressanone, XXI, pp. 99-108,
2005.
Dei, L., Favaro, M., Giorgi, R., Portieri, R., Gli stucchi della Cappella della
Madonna di Lourdes nella Chiesa di S. Giovanni Evangelista in Venezia:
caratterizzazione del degrado e pre-consolidamento mediante dispersioni
alcoliche di calce, In: National Congress Scienza e Beni Culturali: Lo
Stucco. Cultura, Tecnologia, Conoscenza, Bressanone, XVII, pp. 557-566,
2001.
Slkov, Z., Drdck, M., Moreau, C., Frankeov, D., Nosl,
L., Consolidation of porous limestone with suspensions of calcium
hydroxide nano-particles in alcohols, In: Stonecore Recent progress in
the consolidation of calcareous materials, Litomyl, Czech Republic,
2010.
Daniele, V., Taglieri, G., Nanolime suspensions applied on natural
lithotypes: the influence of concentration and residual water content on
carbonatation process and on treatment effectiveness, Journal of cultural
heritage, 11, pp. 102-106, 2010.
Ambrosi, M., Giorgi, R., Salvadori, B., Dei, L., Nanotecnologie per la
conservazione di affreschi e materiali lapidei a base carbonatica, In: 1st
International Workshop on Science, Technology and Cultural Heritage,
Venezia, pp. 29-33, 2004.
Hansen, E., Doehne, E., Fidler, J., Larson, J., Martin, B., Matteini, M., et
al., A review of selected inorganic consolidants and protective treatments
for porous calcareous materials, Rev Conserv., 4, pp. 1325, 2003.
http://www.italithos.uniroma3.it/index.php.

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Materials Characterisation V

67

Nanocarbon composite materials with


optical response on radioactive waste
M. Vantsyan1, G. Popova1, E. Karpuzova1, M. Bobrov1, O. Plaksin2
& E. Dabek3
1

D. Mendeleyev University of Chemical Technology of Russia, Russia


A.I. Leypunsky Institute for Physics and Power Engineering, Russia
3
Science & Technology Branch Environment Canada, Ottawa, Canada
2

Abstract
Nanocarbon materials have numerous unique features high porosity, large
specific surface area, chemical inertness, radiation stability, etc. We applied
nanocarbon/nanodiamond and silicon carbidecomposites as matrix for optical
chemochips construction. Composite elements consist of porous nanocarbon
substrate with specific chromophores introduced to nanosize pores and siliconorganic coating. Similar multicomponent composition has a response to
radiation, in particular, -irradiation. By using diarylethenes as sensitive
chromophores, their electronic and/or luminescent spectra data may be applied
for doze power detection. Quantum chemistry methods, computer simulation
were considered for optimal design of nanocarbon/organic chromophore hybrid.
Experimental data and modeling have shown that diarylethenes are able to
change color under -irradiation in molecular crystal phase only. Weak
interactions (inter-, intramolecular and binding with hydrogen-containing walls
in pores) play key role under irradiation. Induced self-organization in limited
volume is considered. SWAXS and AFM data are discussed. Nanodiamond
composition possesses luminescent response to -, - and -irradiation. Siliconorganic polymer and SiC composition are neutral to irradiation, they are stable in
extreme conditions. Application of composite elements with optical sensing as
multifunctional chemochip fragment for atmospheric media monitoring is
discussed.
Keywords: nanocarbon, nanodiamond, silicon, composite, chemochip,
chromophore, radiation, computer simulation, optical response, nuclear waste.

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68 Materials Characterisation V

1 Introduction
One of the most important directions of modern nanoscience and
nanotechnology is the so-called sensor technology combining the latest
achievements in highly sensitive intelligent materials, first of all, multifunctional
chemochips with immobilized sensing fragments with nanoscale function [14]
and different microdevice construction with high processing speed and
reliability. Of especial interest are the materials with high sensitivity and
adaptability [5]. In this context, great attention is being given to the selfassembling systems capable of hierarchical ordering from the nano- to
mesoscopic level [6], which may lead to elaboration of intelligent, in particular,
optically sensing, materials responsive to weak external factors such as
temperature, irradiation, pH, pollutants in the environment, etc. Typically, these
devices (chemochips) consist of solid inorganic support and sensing fragments
immobilized on it.
Nanocarbon materials are promising inorganic supports as they have a large
variety of unique and specific properties high porosity, large specific surface
area, chemical inertness, radiation stability and others [7]. To date, highly porous
(up to 40% vol.) composites can be prepared on the basis of nano-sized diamond.
Diarylethenes seem to be the most suitable objects to be used as sensing units.
These are photochromes changing from colourless to coloured under irradiation; normally, the colour disappears upon UV or visible-light irradiation
[8]. Diarylethenes have numerous advantages such as thermal stability, linear
dose dependence of the coloration, compared to other photochromic compounds.
On the other hand, diarylethenes exhibit their sensing properties in highly
ordered state (e.g. in single crystal). In this context, of great importance is
prediction of diarylethene molecules self-organization pattern.
Computer modeling and quantum chemistry calculations help greatly to
successfully solve applied science problems of predicting optimal synthetic
pathways, structure and properties of materials resulting in decrease in time and
costs of initial laboratory investigations. For integrated solution of the problem it
was necessary to predict diarylethenes self-organisation in a limited volume i.e.
to estimate the possibility for chromophores introduction into porous composite
and to evaluate the assembly parameters.
In this study, we applied experimental techniques together with a set of up-todate computing chemistry methods, Cambridge Structural Database and
specialized software. We obtained models of diarylethene molecules and their
assemblies; non-covalent interactions providing formation of 2D and 3D
supramolecular clusters and crystal structures were revealed.

2 Results and discussion


In this study, for multifunctional detector device creation we used
efficient adsorption properties of nanoporous carbon composites
nanocarbon/nanodiamond and silicon carbide [9, 10] subsequently covering the
composite matrix with polymeric photochromic composition.
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Materials Characterisation V

69

As nanodiamond composite matrix is black it is reasonable to introduce only


luminescent molecules whereas silicon carbide composites are suitable for
colour-changing chromophores. Therefore, we applied diarylethenes that change
both luminescence and colour under different types of irradiation. Moreover,
diarylethenes (DAE) have a unique property to change their colour under
radioactive irradiation and to reversibly restore it under UV-irradiation. We have
chosen a diarylethene 1,2-bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene
changing from colourless to coloured under -irradiation; the colour disappears
upon UV or visible-light irradiation [11] (Fig.1).
F

F
F
F

F
F

H 3C

CH3
H3C

Open form
colourless

Figure 1:

F
F

F
F

UV or visible-light
irradiation

CH3
H3C

-irradiation

CH3
S H3C

CH3

Closed form
coloured

Coloration under -irradiation and bleaching under UV or visiblelight irradiation.

Nanodiamond/nanocarbon composites samples were black tablets with


diameter of 8 mm and thickness of 3 mm. They contained 28% vol.
nanodiamond, 15% vol. graphite-like carbon with porosity of the material 57%
vol. and pore size 8 10 nm (as found by capillary condensation method).
Silicon carbide nanocomposite samples were grayish tablets with a diameter
of 8 mm and thickness of 3 mm. Composites surface was studied by atomic force
microscopy method (AFM); the average pore size was found to be up to 10 nm
[10]. However, pore shape and depth was not estimated with high accuracy.
Theoretically, different pores in composites can have conic and cylindrical
shape. For calculations we used an approximation that all pores in composites
are cylindrical with pore diameter not more than 10 nm.
Average grain size of the composites was estimated by wide-angle x-ray
scattering method (WAXS). For nanodiamond/nanocarbon composite it was 4
nm, for silicon carbide 12.5 nm.
Chromophores were introduced by impregnation method: composites were
treated by 2% mass solution of diarylethene in chloroform with subsequent
drying under vacuum.
Luminescence spectra of modified nanoporous matrices exhibit a new
emission band corresponding to starting diarylethene. The intensity of this new

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70 Materials Characterisation V
band is approximately 1520% from intensity of the luminescence peak of
starting diarylethene.
A preliminary study has shown rather high radiation stability of nanocarbon
composites , silicon-organic coating and chromophores.
Diarylethene molecules are conjugated aromatic systems capable not only of
hydrogen bonding but also of stacking interactions [12]. Pore size and shape also
influence self-organization of chromophores when filling the limited volume.
A molecular geometry modeling for diarylethene molecule and for its
molecular aggregates was performed by semi-empirical quantum chemistry
methods 1 by programme complex GAMESS [13]. The initial approximation
of the molecule (derived from x-ray diffraction data) was taken from Cambridge
Structural Database [14]. After optimizing the geometry parameters of
diarylethene molecule, we have estimated maximal distances between atoms
centres along the axes of three main inertias. These distances were ~9,9 (along
axis 1), ~11,5 (along axis 2), ~6,6 (along axis 3)
The optimization of geometry parameters of two diarylethene molecules
assembly was performed by non-empirical quantum chemistry method GAMESS
DFT 6-31G(d,p) [13]. These methods are also suitable for calculation of bond
critical points, in particular, bond critical points of non-covalent interactions
[15].
The size of the optimized model of the molecular aggregate including two
chromophore molecules (Fig. 2) have also been estimated by maximal distances
between atom centres along three axes. Two diarylethene molecules are arranged
in two parallel planes and are bonded by weak bonds. One can assume two
probable aggregate structures one is formed by four FH bonds and the
other by two SH bonds. Both aggregates dimensions are close to one
another these are 19* 11* 9 .
The proposed four chromophore molecules aggregate structure (Fig. 3) has
maximal distance between atom centres along one of the axes, equal to 29 .
The distance along two other axes is 18 and 9 .
As a result of the calculation performed, it was found that two diarylethene
molecules are also arranged in two parallel planes. In order to reveal weak noncovalent interactions in two diarylethene molecules assembly we have applied R.
Bader quantum topological analysis of atoms in molecules [15]. By programme
complex AIM-2000 bond critical points were calculated and a molecular graph
was drawn for two diarylethene molecules assembly [16]. We have calculated
bond critical points between carbon atoms, distances and angles of weak noncovalent interactions, local characteristics in critical points (Table 1). This
calculation has elucidated weak bonds between fluorine and hydrogen atoms,
these bonds are pairwise symmetrical. Moreover, weak bonds were found inside
the molecule, by bonds fluorine hydrogen an intramolecular cycle is formed.

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Materials Characterisation V

71

(a)

(b)
Figure 2:

Assemblies of two diarylethene molecules; (a) formed by four


FH bonds, (b) by two SH bonds. Non-covalent bonds are
shown by dotted line.

Table 1:

Distances, angles, and local parameters in critical points (3,-1)


corresponding to weak interactions.

CP
number
1
2
3
4
5
6
7
8
9

2.54
2.53
2.53
2.54
2.60
2.60
2.78
2.78
4.20

Angle,
degrees
139.5
146.8
146.8
139.4
108.5
108.5
138.3
138.3
-

Contact
CH38F45
CH38F47
CH77 F8
CH77 F6
CH61F47
CH22 F8
CH22H70
CH38C23
C21C60

CP
number
55
48
52
35
36
24
43
47
33

2b

gb

vb

Econt

a.u.

a.u.

a.u.

a.u..

kcal/mole

0.00636
0.00645
0.00645
0.00635
0.00677
0.00677
0.00195
0.00195
0.00117

0.02822
0.02825
0.02825
0.02822
0.03319
0.03320
0.00619
0.00619
0.004150

0.005769
0.005794
0.005794
0.005768
0.006470
0.006471
0.001114
0.001114
0.0007669

0.004483
0.004525
0.004525
0.004482
0.004642
0.004642
0.0006811
0.0006811
0.0004963

1.41
1.42
1.42
1.41
1.46
1.46
0.21
0.21
0.16

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72 Materials Characterisation V

(a)

(b)
Figure 3:

Assemblies of four diarylethene molecules: (a) formed by two


SH bonds and eight FH, (b) by four SH bonds and
four FH bonds.

Energies of the above mentioned interactions were estimated by local density


of the potential energy (b) in a critical point. For this, an empirical formula was
used: E (kcal/mole) = 313.754vb (atomic units) [17]. So, the overall energy of
interatomic non-covalent interactions was Econt = -9.15 kcal/mole.

3 Conclusions
Experimental techniques (e. g. AFM, x-ray scattering and others) applied
together with a set of up-to-date computing chemistry methods aided greatly for
subsequent creation of a chemochip sensitive to -irradiation based on
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Materials Characterisation V

73

nanocarbon composites. Computer modeling has revealed the self-organization


pattern for diarylethene molecules in limited volume. Diarylethene molecule
dimensions (as well as those for its aggregate of two and four molecules
calculated by semi-empirical quantum chemistry methods) are estimated.
By density functional theory geometry parameters in assembly of two
diarylethene molecules were optimized. The quantum-topological electron
density analysis has revealed weak non-covalent interactions fluorine-hydrogen,
carbon-hydrogen, carbon-carbon. In separate diarylethene molecules a cycle
formed by non-covalent interactions fluorine-hydrogen is found. The overall
energy of interatomic non-covalent interactions was E = -9.15 kcal/mole.
Quantum chemistry and quantum topological analysis methods are promising
tools for revealing interatomic interactions when studying formation of
molecular assemblies at the nanoscale in pore filling modeling.

Acknowledgements
The research is being supported by Ministry of Education and Science or
Russian Federation (Project 2.2.2.2.325) and ISTC (Project #3891).

References
[1] Al-Azzawi A. (ed). Photonics: Principles and practices, CRC Press: Boca
Raton, 2007.
[2] Davies A.G. and Thompson J.M.T. (eds). Advances in nanoengineering:
Electronics, materials and assembly, Imperial College press: London, 2007.
[3] Fryxell G.E. and Cao G. Z. (eds). Environment application of
nanomaterials Synthesis, sorbents and sensors, Imperial College Press:
London, 2007.
[4] Lu G.Q. and Zhao X.Z. (eds), Nanoporous materials: Science and
Engineering, Imperial College Press: London, 2004.
[5] Ong K. G., Yang X., Mukherjee N., Wang H., Surender S., Grimes C.A. A
wireless sensor network for long-term monitoring of aquatic environments:
Design and implementation, Sensor Letters, 2 (1), pp. 48-57, 2004.
[6] Grimes C.A, Dickey E.C., Pishko M. V., Encyclopedia of Sensors, ASP
Press: N.-Y., 2004.
[7] Seki Y., Impact of low activation materials on fusion reactor design,
J. Nucl. Mater, 258-263, pp. 1791-1797, 1998.
[8] Irie S., Irie M., Radiation-induced coloration of photochromic
dithienylethene derivatives in polymer matrices, Bull. Chem Soc. Jpn., 73,
pp. 2385-2388, 2000.
[9] Lisichkin G.V. (ed.) Chemistry of Grafted Surface Compounds, Fizmatlit:
Moscow, 2003.
[10] Gordeev S.K., Nanocarbon Materials, Nanotechnics (Rus.), 2005, pp. 3-11.
[11] Morimoto M., Kobatake S. Irie. M., Photochromism of diarylethenes in
nanolayers of a single crystal, Photochem. Photobiol. Sci., pp. 1088-1094,
2003.
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74 Materials Characterisation V
[12] Yamada T., Kobatake S., Muto K., Irie M., X-ray Crystallographic Study
on Single-Crystalline Photochromism of Bis(2,5-dimethyl-3-thienyl)
perfluorocyclopentene, J. Am. Chem. Soc., 122, pp. 15891592, 2000.
[13] http://classic.chem.msu.su/gran/gamess/index.html.
[14] CSDB, http:// www.ccdc.cam.ac.uk
[15] Bader R., Atoms in Molecules: A Quantum Theory, Oxford University
Press, 1994.
[16] http://www.aim2000.de
[17] Espinosa E., Alkorta I., Rozas I., Elguero J., Molins, E., Topological
Analysis of the Electron Density Distribution in Perturbed Systems. I.
Effect of Charge on the Bond Properties of Hydrogen Fluoride, Chem.
Phys. Letts., 336, pp. 457-464, 2001,.

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Section 3
Corrosion problems

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Materials Characterisation V

77

Evaluation of the fretting corrosion


mechanisms on the head-cone interface
of hip prostheses
I. Caminha1, C. R. M. Roesler2, H. Keide1, C. Barbosa1, I. Abud1
& J. L. Nascimento1
1

Laboratory of Characterization of Mechanical and Microstructural


Properties, National Institute of Technology (INT), Rio de Janeiro (RJ),
Brazil
2
Laboratory of Biomechanical Engineering, University Hospital,
Federal University of Santa Catarina (UFSC), Brazil

Abstract
Fretting-corrosion is one of the main concerns in the application of hip
prosthesis. This type of information is very important in the stage of orthopedic
implants design, with the purpose of minimizing the amount of tissue exposed to
corrosion products which are released during the permanence of the prosthesis in
the patient. The residual corrosion products of stainless steels are associated to
the occurrence of several adverse reactions in the human body. The knowledge
about these corrosion products is extremely important in the phase of the project
of hip prostheses, aiming at the minimization of the amount of exposure of the
organic tissues to corrosion products released during the permanence of the
prosthesis inside the patient.
In the present work the mechanical stability and fretting corrosion resistance
of modular hip prosthesis, which was fabricated with ASTM F 138 austenitic
stainless steel, were evaluated according to the criteria of ASTM F 1875
standard, method I, which prescribes long term test, with the purpose of
determining the amount of damage through the quantification of the corrosion
products and debris which resulted from the fretting corrosion conditions. The
mechanical tests were performed in a servohydraulic mechanical testing machine
and the modular interfaces were exposed to an electrolytic 0.9% NaCl in distilled
water solution and subjected to a minimum load of 230 N and a maximum load
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78 Materials Characterisation V
of 2.3 kN, frequency of 5 Hz for 10 million cycles, according to ASTM F 1875
standard, thus simulating real conditions of use. Load ratio (R = 10) was
determined in ASTM F1440 standard. A significant amount of fretting-corrosion
products were observed: 0.22 g resulted from five specimens after 107 million
cycles, and the diffraction X-Rays tests showed the presence of the crystalline
phases Fe2O3, Fe3O4 and Cr2O6.
It can be concluded that the mass loss in the head-cone connection allowed
the entrance of the physiological saline solution in the inner region of the head,
increasing the predicted micro movement in the headcone interface, resulting in
an accelerated process of fretting-corrosion, and consequently the liberation of
debris and corrosion products that could lead to adverse biological reactions.
Keywords: fretting corrosion, hip prosthesis, modular components, mechanical
properties.

1 Introduction
The increasing life expectancy in the last decades and trauma risk due to the
more frequent exposure of individuals to different types of accidents and current
insecure life conditions has led to an increased search for orthopedic implants
with high performance, capable of resisting to even more severe loads for longer
times. For this reason, metallic materials, which were developed for applications
in orthopedic implants, must present some specific properties, such as
biocompatibility, strength and resistance to degradation (by wear or corrosion).
In spite of the increasing use of titanium and its alloys for this application in
the last decades, in Brazil ASTM F138 austenitic stainless steel [1, 2] is still very
used in the fabrication of modular components for total hip arthroplasty due to its
lower cost, together with good mechanical properties and satisfactory corrosion
resistance, since the main customer is Health Ministry, which supplies the
demands of public hospitals in Brazil.
The use of modular components in the total hip arthroplasty presents several
advantages, such as a great variety of stem geometry, which allows a better
choice of modular component for the surgeon, according to the patient disease,
mainly in the case of revision surgeries, thus minimizing the risk of inadequate
procedures.
However, the modular interfaces are subjected to micro movements, which
can result in fretting and corrosion, leading to the release of debris, which can
cause adverse reactions and accelerated wear in the articulation interface.
Fretting can be defined as a wear phenomenon which occurs when two solids
in contact are subjected to tangential oscillatory movement with small
displacement amplitude. It can be described more accurately as a movement
whose amplitude is smaller than the contact extent. The presence of a corrosive
environment contributes to accelerate the wear process and this condition is
defined as fretting-corrosion. The occurrence of corrosion results in
degradation processes which reduce the structural integrity of the implant and
release products whose reaction can be harmful in contact with organic tissue.

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When the prostheses are fabricated with ASTM F138 stainless steel, the
generation of a passive barrier in the surface (passive layer) is the main obstacle
to corrosion process. This film, which is composed by metallic oxides, formed
spontaneously on the metal surface, and whose thickness can be increased with
surface treatments, avoids the migration of metallic ions from the metal to the
solution and the migration of anions from the solution to the metal through the
metal-solution interface (physiological environment). For being effective barriers
these films must be compact and cover completely the metallic surface, they
must have an atomic structure which limits the migration of metallic ions and/or
electrons through the metallic oxide/solution interface, and they must be capable
of remain on the surface of these alloys even when subjected to mechanical and
abrasive stresses in the clinical use of prostheses.
The most frequently mentioned mechanisms of failure in these components
are aseptic loosening, periprosthetic osteolysis and metallosis and are directly
related to the debris released by the prosthesis components, mainly the non
cemented prostheses [3].
According to the literature [4], the residual products of corrosion in stainless
steel based implants are associated to tissue necrosis, inflammation, allergenic
reactions and even cancer.
The aim of the present work is an evaluation of fretting corrosion in modular
prostheses fabricated with ASTM F 138 stainless steel, in order to minimize the
adverse reactions during the permanence of the prosthesis in the patient.

2 Material and methodology


In this work five modular hip prostheses, composed by heads and stems, five
stems and five heads, fabricated with ASTM F 138 from the same batch, were
analyzed. A SZX16 model Olympus stereomicroscope was used for comparing
the surfaces of the modular components before and after fretting corrosion test.
In Fig.1 an as received representative sample of the batch can be observed.

Head
Figure 1:

Cone

Stem

Head and stem of the hip prosthesis fabricated with ASTM F 138
stainless steel.

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80 Materials Characterisation V
The fretting corrosion tests on the cone-head interface were performed
according to method I of ASTM F 1875 standard, which prescribes a 0.9% NaCl
physiological saline solution, thus simulating in vivo conditions, since that when
implanted in patients these components are in contact with body fluids. With the
purpose of analyzing both fatigue resistance of hip stems and mechanical
stability of modular components the experimental procedures described in
ASTM F 1440 [5] and ISO 7206-4 [6] were also adopted.
These tests were performed in two universal machines for mechanical testing
(Instron model 8872) with a 25 kN load cell with the following characteristics,
described in ASTM F 1875 standard [7]:
-

Maximum load: 3.3 kN;

Frequency: 5 Hz;

Test finish after 10 million cycles;

Error of applied load lower than 1% of the maximum load;

Control function of cyclic load (sinusoidal);

Monitoring of vertical displacement of the prosthesis head and


registering of cycles counting;

Computerized operation;

Equipment for recirculation and heating of solution test with


temperature control within 37C1C.
Before starting the test each modular component composed by head and stem
was prepared according to the following procedure:
- Assembling the modular component and checking the fittings;
- Placing the modular component in a device which allows alignment of
angles referred in the standard, in concern to the load direction;
- Drying the mounting;
- Introducing the environment chamber together with the metallic cup with
the mounted prosthesis;
- Adding the saline solution (0.9% NaCl in distilled water) to the
environment chamber;
- Starting the pump for recirculation and heating the test solution;
- Fitting the complete assembly in the test machine (Fig. 2).
The machine was programmed for the application of the load in the center of
the prosthesis head, with minimum 0.3 kN and maximum 3.3 kN loads, with
sinusoidal 5 Hz frequency according to the conditions specified in ASTM F1875
standard. Maximum load requirements are specified in ISO 7206-4-2010
standard.
A limiting condition was imposed for automatically stop ping the machine: a
vertical displacement of 5 mm. If this value is not reached the test is finished
after completing 10 million cycles of loading and unloading. The parameters of
sample placement follow the requirements of ASTM F1440 standard.
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Materials Characterisation V

Figure 2:

81

Complete assembly before starting test in INSTRON 8872


machine.

X-ray diffraction analysis was carried out in the following conditions: anode
material: Cu K, angle between 10 and 100, step size 0.05, scan step time: 1 s,
receiving slit size: 0.03 mm, current: 40mA, voltage: 40 kV.

3 Results and discussion


The images of the modular surfaces (head and cone), which were obtained by
optical microscopy, did not present surface defects such as cracks other types of
flaws, introduced by the fabrication process, which could influence the results of
this test. In Figs. 3 and 4 the aspect of the surface of the modular components (head
and cone) of a hip prosthesis, before and after testing, are presented. The other
prostheses have similar aspects. A significant corrosive attack inside the head and
in the cone can be observed after 1 million cycles with increasing rates along the
test, releasing corrosion products which resulted in mass loss in the head-cone
connection. The mass loss, which was observed in the test solution, allowed the
introduction of saline solution inside the head, increasing the predicted micro
movements, leading to an accelerated wear (friction), with tearing of debris,
according to Fig. 6. No type cracks and mechanical failure could be observed in
the five hip prostheses, which were analyzed, thus meaning that the mechanical
stability of the modular component was preserved along the test.

Figure 3:

Detailed view inside the heads: (a) before and (b) after the test.
Magnification: 10X.

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82 Materials Characterisation V

Head-cone interface

Figure 4:

Detailed view of the cone region: (a) before (b) after.


Magnification: 10X.

Figure 5:

Detailed view of the head-cone interface connection shown in Fig.


4-b. Magnification: 60X.

Figure 6:

Detailed view of tearing which was observed on the cone.


Magnification: 60X.

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Materials Characterisation V

83

In Figs. 7 and 8 the corrosion products and particulate residues (debris),


resulting from the fretting corrosion test can be observed in the bottom of the
environment chamber (indicated by an arrow in fig. 8). These ones are
consequence of the damages caused by fretting and corrosion fretting in the
head-cone interface of the primary hip prosthesis. These images represent the
five hip prostheses subjected to this analysis.

Figure 7: Test assembly after 106 cycles.

Figure 8: Detail.

Until 1 million cycles neither corrosion products nor particulate debris could
be observed, but after this period the degradation of the modular component was
increasing and localized on the head-cone, as can be seen in detail in Fig. 5.
After 10 million cycles the corrosion products and particulate debris were
quantified, resulting in an average value of 0.22 g. In the literature there is only
one citation of fretting-corrosion products quantification, but in their experiment
the cycle number was varied, thus hindering any type of comparison with the
results presented in this work.
For better comprehension of fretting corrosion mechanisms in hip modular
components the variation of load and number of cycles is necessary. The
characterization of the corrosion products and particulate residues by X-ray
analysis is also very important, in order to identify the phases and type of
metallic particles which were released, with the aim of minimizing the incidence
of aseptic loosening, periprosthetic osteolysis and metallosis in the surgeries of
total hip arthroplasty. In the present work a complete characterization of the
fretting corrosion products was not concluded, but it can be observed that they
presented a predominantly ellipsoidal shape with size distribution approximately
uniform, whose larger diameter was around 500 m.
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84 Materials Characterisation V
Anyway, the X-ray diffraction analysis performed in the corrosion products
showed the presence of the following crystalline phases: Fe2O3, Fe3O4 and
incipient Cr3O8, compatible with the ASTM F138 stainless steel.

4 Conclusion
The evaluation of fretting corrosion on the head-cone connection interfaces of
five modular hip prosthesis fabricated with stainless steel led to the following
results:
A significant grade of localized corrosion in the inner region of the head
and in the head-cone interface was observed, originated from the
fretting corrosion and fretting during 10 million cycles, resulting in
particulate debris and corrosion products.
In order to achieve a better comprehension of the fretting corrosion
mechanisms, more tests are necessary, including changes in the applied
load and number of cycles.
At first glance, fretting corrosion does not affect the mechanical
stability of the modular components, at least until 107 cycles.

References
[1] Cavalcanti, E.H. de S., Souza, S.M.C. de, Ferreira, C. de A., Campos, M.M.,
Abud, I. de C. and Palmeira, L., (2002), Avaliao da Resistncia
Corroso de Prtese Total de Quadril de Ao Inoxidvel Austentico
Removida de Paciente, 22 CONBRASCORR Congresso Brasileiro de
Corroso, Salvador Bahia.
[2] Giordani, E.J., Ferreira, I. and Balancin, O., (2007), Propriedades
mecnicas e de corroso de dois aos inoxidveis austenticos utilizados na
fabricao de implantes ortopdicos, REM: R. Esc. Minas, Ouro Preto,
60(1): 55-62.
[3] Crestani, M.V., Boschim, L.C. and Schwartsmann, C.R., (2004), Metalose
Simulando Tumor Abdominal , Revista Brasileira de Ortopedia, Nov/Dez.
2004.
[4] Merritt, K.; Brown, S.A.; (1985), Biological Effects of Corrosion Products
from Metals, Corrosion and Degradation of Implant Materials: Second
Symposium, ASTM STP 859, A.C. Fraker and C.D. Griffin, Eds., American
Society for Testing and Materials, Philadelphia, 1985, pp. 195-207.
[5] ASTM F 1440 92 (Reapproved 2008), Standard Practice for Cyclic
Fatigue Testing of Metallic Stemmed Hip Arthroplasty Femoral Components
Without Torsion.
[6] ISO 7206-4-2010 - Implants for surgery - Partial and total hip joint
prostheses -- Part 4: Determination of endurance properties and performance
of stemmed femoral components.
[7] ASTM F 1875 98 (Reapproved 2004), Standard Practice for Fretting
Corrosion Testing of Modular Implant Interfaces: Hip Femoral Head-Bore
and Cone Taper Interface.
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Materials Characterisation V

85

Improving corrosion performance by


surface patterning
M. Bigdeli Karimi, V. Stoilov & D. O. Northwood
Department of Mechanical, Automotive and Materials Engineering,
University of Windsor, Canada

Abstract
Based on the idea that hydrophobic (low or non-wettable) surfaces can decrease
the contact area between a corrosive solution and a surface, thereby potentially
rendering the material more corrosion resistant, the effect of surface patterning
on the corrosion behaviour of nickel was investigated. The surface patterning
consisted of an array of holes of various diameters (D) and inter-hole spacings
(L) that were produced by a laser ablation process. The corrosion behaviour of
the patterned surfaces was studied using a potentiodynamic polarization method
in a 0.5M H2SO4 electrolyte and compared with that of a polished reference
sample. Following the potentiodynamic polarization corrosion test cycle, the
corroded surfaces were examined using scanning electron microscopy (SEM) for
morphological features and white light interferometry (WLI) to determine the
surface roughness. The changes in surface morphology were related to the
corrosion behaviour. A relationship was found between D, L, and the corrosion
current density (Icorr), whereby the higher the (D/L )2 ratio, the higher the Icorr
value. The corrosion potential (Ecorr) of all surface patterned samples was lower
(less noble) than that of the reference sample in all tests.
Keywords: corrosion resistance, surface patterning, hydrophobicity, laser
ablation.

1 Introduction
Wettability of solid surfaces is an important property and depends both on the
surface chemistry and on the surface topology. Recently, hydrophobic and
superhydrophobic surfaces (water contact angles larger than 150) have received
a lot of attention, due to their important applications ranging from self-cleaning
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86 Materials Characterisation V
materials and in-flight icephobic treatment [1] to microfluidic devices. The
archetype superhydrophobic surface is that of the lotus leaf, on which a water
droplet apparently forms a sphere, reducing the area of contact. This behavior,
known as the lotus-leaf-effect, is found to be a result of the hierarchically
patterned structure. Effectively the fluid cannot penetrate the air gaps between
the patterned pillars on the surface, and therefore it forms a heterogeneously
wetted contact surface of alternating liquid/solid contacts and air pockets. As a
result the overall solid liquid contact area is significantly reduced [25].
In the present work we employ surface patterning to create heterogeneous
wetting on metallic surfaces. We show that heterogamous wetting in metallic
surfaces leads to reduction in corrosion rates and increase in corrosion resistance.

2 Experimental procedures
2.1 Specimen preparation
Pure nickel (99.7 Wt.%) was selected as a model metal. Samples of 1.5 cm 1.5
cm size were polished to a standard finish with a roughness that did not exceed
50 nm. Laser ablation with a single pulse copper bromide (CuBr) metal vapour
laser was used to create special surface textures. During laser ablation, nitrogen
(N2) was blown to protect the surfaces from oxidation and clean any debris. The
pulse duration was selected at 30 ns. Different hole/pattern sizes were achieved
with different laser output power within the range of 20-80 W. Figure 1 shows a
schematic of the applied pattern. The diameter of the holes and the inter-hole
spacing were varied to obtain different textures. Table 1 presents the selected
hole size and the inter-hole spacing. The distances between the holes are labeled
L1, L2 and L3, where as the D1, D2, D3 etc are the hole diameters.

Figure 1:

Schematic presentation of the proposed surface texture; D relates to


the hole diameter and L defines the inter-hole spacing.
Table 1:

Hole diameter
(D) m
5
10
20

The hole sizes and inter-hole spacing.


Inter-hole
spacing
L1, m
5
10
20

Inter-hole
spacing
L2, m
10
20
30

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Inter-hole
spacing
L3, m
20
30
40

Materials Characterisation V

87

For easy identification of the samples the following sample labeling system
has been adopted: DxLy, where x is the diameter of the hole in m and the y is
the inter-hole spacing in m.
2.2 Corrosion tests
The corrosion resistance of the samples was determined using a potentiodynamic
polarization corrosion test, wherein the samples were immersed into a 0.5M
H2SO4 solution at room temperature (24 C). A conventional three-electrode
system was used in which a standard calomel electrode (SCE) served as the
reference electrode and a platinum electrode as a cathode electrode. In the tests,
the applied potentials were in the range of -0.7 to 1.5 V (with respect to SCE)
with a scan rate of 1.0 mV/s. Corrosion rates were calculated in terms of the
corrosion current density, Icorr, by using linear polarization resistance curves
(LPR). The relationship between Icorr and the polarization resistance, Rp, is
obtained from the StearnGeary equation [5]:

Rp
where a and

a c
E

iapp 2.3( I corr )( a c )

(1)

are the Tafel slopes of the anodic and cathodic reactions,

respectively, Icorr is the corrosion current density and the

E
is polarization
iapp

resistance. After the corrosion test the sample surfaces were examined using
JEOL 5800 scanning electron microscopy (SEM), and energy-dispersive X-ray
spectrometry (EDS).

3 Results and discussion


3.1 Corrosion tests
The electrochemical characteristics of the patterned Ni samples were
investigated by potentiodynamic techniques described in Sec 2.2. Polarization
curves for all patterned samples and the reference sample were analyzed and the
corresponding corrosion current density, Icorr, and potential, Ecorr ,were obtained.
Figure 2, shows the variation of the Icorr for different hole diameters (1/D) in
samples with the same ratio of patterned to non-patterned area (D/L)2. Clearly
samples with D=10 m(1/D=0.1 m-1) have the worst corrosion properties
compared to any other samples with either pattern density((D/L)2=0.25 and
(D/L)2=1.0). On the other hand, samples with D=20 m(1/D=0.05 m-1) show
the lowest Icorr , and therefore better corrosion resistance at either pattern density.
In addition, the corrosion resistance observed in samples with D=20 m exceeds
the performance of the reference sample (1/D=0.0 m-1) which is a significant
improvement of the corrosion properties of the metal surface. The observed
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88 Materials Characterisation V
trends in Figure 2 suggest that a decrease of the hole size (D) m towards nanoscale size could decrease the corrosion current density, Icorr, even further.
Figure 3 presents the Ecorr values for samples with pattern density of (D/L)2=1
and (D/L)2=0.25. The corrosion potential (Ecorr) of all surface patterned samples
was lower (less noble) than that of the reference sample (1/D=0.0 m-1) in all
tests.

a)

b)

Figure 2:

The Icorr values versus inverse hole diameters (1/D) for all samples
with (D/L)2=1 and (D/L)2=0.25 after the corrosion test.

a)

b)

Figure 3:

The Ecorr values versus inverse hole diameters (1/D) for all samples
with (D/L)2=1 and (D/L)2=0.25 after the corrosion test.

3.2 SEM images after corrosion tests


The patterned samples were examined by SEM before and after above corrosion
tests (see Figs. 46). The original REF sample showed some severe, localized
corrosion. It is evident that those areas were formed by coalescence of small
pits.
Sample D10L30 showed a severe corroded appearance (Figs. 5a and 5b).
According to Icorr of this sample there is a good agreement between corrosion
current density and the surface condition.

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Materials Characterisation V

a)

89

b)

Figure 4:

a)

SEM images of the reference sample(REF) a) before and b) after


corrosion testing.

b)

Figure 5:

a)

SEM images of the D10L30 a) before and b) after corrosion testing.

b)

Figure 6:

SEM images of the D20L40 a) before and b) after corrosion testing.

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90 Materials Characterisation V
Sample D20L40 exhibited the lowest amount of patterning degradation.
Comparing the original sample and after the corrosion test there was no obvious
change of the surface pattern [Figures 6(a) and 6(b)]. The measured Icorr for this
sample was the lowest of all samples including reference and patterned. No
surface damaged was detected also in samples D20L20 and D20L40. Clearly the
observed surface damage in all samples was in a good agreement with the
predicted trends by the measured Icorr values.

Sample REF

a)

Sample REF

b)
Figure 7:

EDS analysis of the reference sample REF a) before and b) after


corrosion testing.

3.3 EDS analysis of the patterned samples


In order to investigate the significant improvement of the corrosion resistance in
some samples energy-dispersive x-ray spectrometry (EDS) was used. The main
goal was to evaluate the change of the O concentration on the surface of the
samples and on the inside of the patterned holes. Fig. 7(a) refers to sample REF
before the corrosion test. In the spectrum three elements, nickel (Ni), oxygen (O)
and carbon (C) are observed. The intensity of the most intense peaks
(Ni: L=0.851 and O: K=0.523 keV) was used to calculate the ratio of Ni/O (see
Fig 7(a)).
Comparing sample REF before the test [Fig. 7(a)] and after the test [Fig. 7(b)]
shows that there is virtually no change in the O concentration on the surface. The
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Materials Characterisation V

91

Ni/O ration remained at 49/5, indicating that passive oxide layer was not formed.
Similar EDS spectra were obtained for all corrosion damaged samples. For
instance the EDS spectra of sample D5L20 on the surface [Fig. 8 (a)] and in the
hole [Fig. 8 (b)] after corrosion testing do not show any significant difference
and the Ni/O ratio is the same as for the polished REF sample. However, the
EDS spectra for the pattered samples with the improved corrosion properties
(D20L20, D20L30, and D20L40) exhibit different behaviour. The Ni/O ratios for
sample D20L40 before and after the corrosion test are shown in [Figs. 9 (a),(b)
and Figs. 10(a),(b)]. The concentration of the O on the surface before and after
the corrosion test slightly changed, which is consistent with the other corrosion
damaged samples.
However, the bottom of the patterned holes shows significant increase in O
concentration (Figs. 8(b) and 10(b)). This clearly indicates that Ni oxides were
formed but were not dissolved by the electrolyte. A possible explanation could
be that the fluid actually did not reach the bottom of the patterned hole. In other
words, in the samples with better corrosion resistance, the contact between the
electrolyte and the metal surface is heterogeneous wetting alternating
solid/liquid zones and air pockets.

Sample D5L20-surface

a)

Sample D5L20-hole

b)
Figure 8:

EDS analysis of the sample D5L20 after the corrosion test


a) surface and b) hole.

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92 Materials Characterisation V

Sample D20L40-surface

a)

Sample D20L40-hole

b)
Figure 9:

EDS analysis of the virgin sample D20L40 a) surface and b) hole.


Sample D20L40-surface

a)

Sample D20L40-hole

b)
Figure 10:

EDS analysis of the sample D20L40 after the corrosion test


a) surface and b) hole.

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Materials Characterisation V

93

4 Conclusions
Surface patterns with different pattern density were successfully created on Ni by
laser ablation. The patterns had a distinct effect on the corrosion properties of the
metallic surfaces. A specific group of patterns led to significant decrease of the
corrosion current density and the corresponding corrosion rate. For this group of
patterns it has been shown that a possible reason for the decrease in corrosion
rate is the detected heterogeneous wetting on the patterned surface.

References
[1] K. Varanasi, T. Deng, J. David Smith, M. Hsu, and N. Bhate, Frost
formation and ice adhesion on superhydrophobic surfaces Appl. Phys. Lett.
Vol. 97, 2010, No 234102.
[2] M. Shafiei and A. T. Alpas, Nanocrystalline nickel films with lotus leaf
texture for superhydrophobic and low friction surfaces, Applied Surface
Science Vol. 256, 2009, pp. 710719.
[3] W. Barthlott and C. Neinhuis, Purity of the sacred lotus, or escape from
contamination in biological surfaces, Planta, Vol. 202, 1997, pp. 1-8.
[4] S.J. Lee, C.H. Huang, J.J. Lai and Y.P. Chen, Corrosion-resistant
component for PEM fuel cells, Journal of Power Sources, Vol. 131, 2004,
pp. 162-168.
[5] T. Liu, Y. Yin and L. Dong, New application of the underwater superhydrophobic surface in the corrosion protection, Advanced Materials
Research, Vols. 79-82, 2009, pp. 1115-1118.
[6] M. G. Fontana and N. D. Greene, Corrosion engineering, 2nd edition,
McGraw Hill, 1978.

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Materials Characterisation V

95

Material characterisation to understand


various modes of corrosion failures in large
military vehicles of historical importance
A. Saeed1, Z. Khan1, N. Garland1 & R. Smith2
1

Sustainable Design Research Centre,


School of Design, Engineering and Computing,
Bournemouth University, UK
2
The Tank Museum, Bovington, UK

Abstract
Large military vehicles within museum collections are stored in two distinct
environments, controlled and uncontrolled, with an intermittent transitional
mode where vehicles travel between the two. Variable environmental conditions
combined with operational factors pose significant risks to the reliability,
durability and longevity of these vehicles. Although there are methods for
retarding or decelerating aspects of failure, to maintain the integrity and
originality of these vehicles as artefacts a sustainable methodology for
conserving these vehicles should be developed.
Corrosion is one of the significant contributors to the structural damage and
material aging of historical military vehicles; therefore an experimental study
was conducted to understand the prevailing mechanisms of failures due to
corrosion with various types occurring in these vehicles identified. This paper
presents various modes of corrosion in historic vehicles while X-ray
Fluorescence and ultrasonic scanning corrosion mapping techniques characterise
corrosion inhibiting materials and subsequent material loss. Understanding
material profiles and their link to environmental exposure during use and non use
of these vehicles will lead to a sustainable methodology for their conservation.
Keywords: sustainable, military, vehicle, corrosion, materials, conservation.

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96 Materials Characterisation V

1 Introduction
The structural and functional deterioration of the large metal structures due to
their environmental exposure and the operating conditions are responsible for
their structural aging [1]. Aging mechanisms in large metal structures such as
bridges, aircrafts, vehicles etc is recognised as a growing problem [2]. Aging
mechanisms such as corrosion, surface and sub surface cracks, wear due to
interacting surfaces and undesired stresses are leading to mechanical failures,
higher maintenance costs and compromises the structural integrity. Corrosion
has been identified as one of the major contributor to the aging mechanisms; it
affects all metal structures by deteriorating the materials properties [3].
This research focuses upon the corrosion damage within the large historic
vehicles in the museum environment. Corrosion is indiscriminate in affecting
metal structures and museum artefacts are no exception. The military vehicles
from World War I and II were designed and manufactured according to the
automotive technologies in place at those times [4] with only a limited lifeexpectancy, however their participation in the war and the subsequent historic
significance means it is important to devise sustainable methodologies for longterm preservation. Continuous corrosion problems within large historic military
vehicles in the museum environment are leading to the concerns of their
longevity, in particular where failures in protective measures are also identified
[5]. For the purpose of sustainable methods it is important to understand the
various corrosion modes, material characterisation and the material loss profile
due to corrosion.
For this research military vehicles were inspected for visual signs of corrosion
and novel methods such as X-ray fluorescence for elemental identification and
ultrasonic scanning for material loss were conducted. Visual inspection
identified different modes of corrosion depending on their exposure to extreme
environments during the war, operating conditions at the time of their service
life, types of materials used and their current working or non-working
environments.
X-Ray fluorescence method found Fe, the main constituent; other elements
such as W, Mo and Mn were also identified. Ultrasonic methods found severe
material loss due to corrosion in the selected samples.

2 Experimental methodologies
The following methods are used in the research. Only the most common and
reoccurring types of corrosion which were found on a larger scale in the vehicles
are presented here.
2.1 Visual inspection
Visual inspection was completed on more than 20 large military vehicles from
the World War I, II and post war era. The investigation found one or more forms
of corrosion in the same vehicles. Some widespread and most occurring modes
of corrosion are described from four military tanks Table 1.
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Materials Characterisation V

Table 1:

97

Military tanks presented in this research.

No

Vehicle

Environment

1
2
3
4
5

Mark II
Sherman*
King Tiger
Centurion
Scorpion

Controlled
Uncontrolled
Controlled
Uncontrolled
Uncontrolled

Manufacture

Country of
Origin

Era

1917
United Kingdom WW 1
1940-1941
United States
WW 2
1943
Germany
WW 2
1945
United Kingdom Post war
1973
United Kingdom Post War

XRF and Ultrasonic scanning is conducted on Sherman.

2.2 X-ray fluorescence


X-ray fluorescence was conducted on Sherman M4A1 for elemental
identification. The test sample was bombarded by an intense x-ray beam
resulting in the emission of fluorescent x-rays from the test object. The emitted
fluorescent x-rays are then detected by XRF analyser [6] which identifies the
elements by measuring the energies of the emitted fluorescent x-rays and
counting the number of rays in each energy spectrum [6, 7].
2.3 Ultrasonic scanning
Ultrasonic scanning uses pulse waves from 0.10 to 15.0 MHz frequencies range
to measure material loss and other dimensional anomalies in the test objects [8].
This research work presents ultrasonic scanning using pulse echo method where
pulses are transmitted and received back on the same side of test object to detect
and characterise defects.

3 Results
3.1 Uniform corrosion
With uniform corrosion a direct chemical attack affects the surface of the metal
and then spreads out evenly across the entire surface, results are not usually fatal
and it is not classified as one of the severe forms [9]. Figure 1 of the King
Tigers flywheel shows uniform corrosion spreading across the surface. Uniform
corrosion was also found in Tog II and FT 17 on considerably larger surface
areas. Uniform corrosion, if left to continue, could lead to general thinning of the
surface and may transform in to another form of corrosion [10].
3.2 Fretting corrosion
Fretting corrosion occurs at the interface of the interacting surfaces which are
subject to relative motions. The King Tiger planetary gears (Figure 2) are a
classic example of this form. Interacting mechanical wear lead to the removal of
material particles, followed by the oxidation of the material debris and the newly
exposed surface [11]. The oxidised debris would act as an abrasive media
leading to further wear and fatigue failures could occur [9, 12].
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98 Materials Characterisation V

Figure 1:

Figure 2:

King tiger flywheel.

King tiger planetary gears.

3.3 Stress corrosion cracking


Stress corrosion cracking is considered one of the severe types of corrosion, it
could cause a partial or complete failure of a structure especially in the presence
of dynamic or static loading and initiation of a stress corrosion crack [13]. The
Mark-II Tank glacis plate in Figure 3 shows stress corrosion cracking where a
crack is initiated and penetrating through the surface with no significant material
loss on the surface. Stress corrosion is difficult to detect, hard to predict and
unexpected failure can occur [13, 14].
3.4 Inter-granular/exfoliation corrosion
Inter-granular corrosion describes the attack on a metals or alloys grains or
boundaries [15]. Corrosion products between the grain boundaries exert pressure
on the grains and the result is exfoliation corrosion. The Centurion armoured
skirt in Figure 4 is an example of exfoliation corrosion leading to lifting or
leafing effect. Leafing or lifting effect is a direct result of the expanding
corrosive products among the grains of the metals which forces the grains apart
[9].
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Materials Characterisation V

Figure 3:

Figure 4:

99

Mark II glacis plate.

Centurion armoured skirt.

3.5 Galvanic corrosion


Galvanic corrosion is the electrochemical reaction between two dissimilar metals
in the presence of electron conductive path and the preferential corrosion of one
metal more than the other [16]. This mode of corrosion was identified in the
Scorpion, see Figure 5. The presence of moisture among the bolt, washer and the
armoured skirt has caused this type of corrosion.
3.6 Pitting corrosion
Centurion in Figure 6 shows signs of pitting corrosion. In this case the corrosion
is confined to a small point with resulting cavities in the metal. The localised
phenomenon of corrosion creates holes in the metal and then penetrates inwards,
deteriorating metal from the inside. The corrosion products covers the pit and
creating a small hole with no significant material loss on the surface leading to a
catastrophic malfunction, it is one of the severe forms of corrosion which is very
difficult to detect and hard to predict the result [14, 17, 18].

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100 Materials Characterisation V

Figure 5:

Galvanic corrosion in scorpion.

Figure 6:

Pitting in centurion.

3.7 X-ray Fluorescence of the Sherman M4A1


X-Ray fluoresce (XRF) was conducted on three points A, B, C on corroded, E, F,
and G on sand blasted surfaces and point D on the cross section of the sample,
see Figure 7. Table 2 shows results of the points A, B and C. On averages Fe
92.07% is the highest, second highest is the Si 5.39%, Mn 0.91% was the third
highest and the lowest was Cu with a trace of 0.04%.
Figure 8 shows the graphical representation of the XRF conducted at point D
where Fe 98.30% is the highest, second highest is Si 0.65%, Mn 0.63% the third
highest and traces of Ti, V, Co and Mo were identified.
XRF conducted at points E, F and G on the sandblasted surface shown on
averages Fe 98.12% the highest, Mn 0.66% second highest, Si 0.59% the third
highest while W 0.02% the lowest and no traces of Co or V were identified.
Figure 9 shows the graphical representation of the XRF analysis at point G.

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Materials Characterisation V

Figure 7:
Table 2:

101

XRF points on Sherman.

XRF of the corroded surface of M4A1.

Vehicle Type: Sherman


Sample- 1
Time duration: 30 seconds

Surface: Corroded
MQ for points: A= 5.70 B= 4.50 C=
4.60
06 American
06 American

Material Standard

06 American

Constituents %

A- Reading 254

B-Reading 255

C-Reading 256

4.89
0.46
0.19
0.05
0.11

5.92
0.54
0.19
0.05
0.08

5.38
0.85
0.2
0.05
0.09

1
2
3
4
5

Si
P
Ti
V
Cr

Mn

0.86

1.11

0.78

7
8
9
10

Fe
Co
Ni
Cu

92.68
0.21
0.06
0.05

91.48
0.22
0.08
0.03

92.05
0.12
0.1
0.04

11
12

Mo
W

0.05
0.33

0.06
0.2

0.06
0.12

3.8 Pulse echo ultrasonic scanning


Pulse Echo scanning was conducted on the Sherman M4A1 with a probe of 4.00
MHz twin crystal and 10.00 mm diameter using 0.25 MHz Hi pass filter and
10.00 MHz low pass filter frequencies with a probe delay of 7.630 S.
Compression waves with a velocity of 5903.00 M/sec are used to scan a total
area of 174.00 mm length with 6.040 pulses/mm and 68.00 mm width with 3.580
pulses/mm mapping material loss every 2.00 mm on the sample.
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102 Materials Characterisation V

Figure 8:

XRF analysis of point D, No Fe (98.30%) included.

Figure 9:

XRF analysis of point G, No Fe (98.09%) included.

Figure 10 shows the end views and the c-scan of the sample with
implementation of colour coding Red for 0.00 mm and Blue for 10.00 mm. Two
cursors Red and Blue show the X-axis, Y-axis location and the corresponding
depths of the particular points on the sample.
A user defined area is taken for finding the maximum and minimum
thicknesses starting at 2.00 mm on the X-axis, 2.00 mm on the Y-axis in
Figure 11 and finishing at 172.00 mm on the x-axis and 66.00 mm at the y-axis
in Figure 12 respectively to avoid any distortion in signals at the edges. The scan
detected maximum remaining thickness of 9.80 mm at horizontal position of
150.00 mm and vertical position of 26.00 mm with a drastic loss in material to a
minimum of 4.60 mm at horizontal position of 28.00 mm and vertical position of
8.00 mm. The maximum thickness of 9.80 mm is recorded at two different
points. The second lowest depth is 4.70 mm and is detected at seven different
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Materials Characterisation V

Figure 10:

Figure 11:

103

Pulse echo scan of M4A1.

User defined area starting at 2.00 mm on x-axis and 2.00 at y-axis.

positions; third lowest of 4.80 mm at six various points and the remaining
thickness of 4.90 mm are recorded at four different points in the samples. The
minimum remaining thickness of 4.60 mm is recorded at three different points.

4 Discussion
The modes of corrosion identified above can be retarded by using the protective
measures such as coatings and paint for uniform corrosion, application of
lubrication and exclusion of air in the fretting corrosion, alleviating the stress in
stress corrosion cracking, using same metal types in galvanic or applying
insulation between two different metals.
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104 Materials Characterisation V

Figure 12:

User defined area finishing at 174 mm on x-axis and 66 at y-axis.

The alloying elements such as Mn, Cr, V W and Mo identified though XRF
are used as hardening agents to improve hardness, ductility and tensile strength
[19]. Also Mo, Mn and P are used for the rust and corrosion prevention. Mo is
used in high strength alloys and super alloys for strength and wear
resistance [20].
Sherman M4A1 was designed by Lima Locomotive Works in the United
States. At the time of manufacture the armoured thickness range was kept
between maximum of 62.00 mm and a minimum of 12.00 mm [21, 22]. However
it is not practical to follow any possible modification in the armour thickness and
because of this reason the highest thickness recorded in the scan is considered
the maximum thickness. During the service life, exposure to extreme
environments has led to the deterioration and material loss. The ultrasonic scan
of has shown a remarkable material loss of 5.20 mm between the maximum
remaining thickness of 9.80 mm and the minimum remaining thickness of 4.60
mm. Currently in the museum collection, the Sherman travels between two
controlled and uncontrolled environments. Varying environments and the
likelihood of failing protective measures, temperature fluctuations, humidity
ratio variations, rain water and the extent of chemical reaction etc will influence
the rate of corrosion and in the controlled environment corrosion residues from
may result in indoor atmospheric corrosion [23, 24].

5 Conclusion
The research work uses a conventional method of analysing corrosion through
surveying vehicles in the museum environment which is followed by novel
methods of XRF for the elemental identification and Ultrasonic scanning to
measure and map corrosion. Research work will be conducted for corrosion
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Materials Characterisation V

105

modelling and for the life expectancy of large historic vehicles based upon the
results from this research work in order to maximise the longevity, durability and
reliability.

Acknowledgements
The authors would like to thank Mark Nel, Mark Clark in AGR, Jon Previtt
West-Dean College and Mike Hayton in The Tank Museum Bovington for their
in kind support during this research work.

References
[1] M. Colavita, "Service Life and Aging of Military Equipment," Corrosion:
Environments and Industries (ASM Handbook), vol. 13C, pp. 220-228,
2006.
[2] A. S. Vinod, "Corrosion in the Military," presented at the Corrosion:
Environments and Industries (ASM International), 2006.
[3] Z. Ahmad, "Basic Concepts in Corrosion," in Principles of Corrosion
Engineering and Corrosion Control, Oxford: Butterworth-Heinemann,
2006, pp. 9-56.
[4] I. C. Handsy and J. Repp, "Ground Vehicle Corrosion," Corrosion:
Environments and Industries (ASM Handbook), vol. 13C, pp. 148-150,
2006.
[5] M. T. Gudze and R. E. Melchers, "Operational based corrosion analysis in
naval ships," Corrosion Science, vol. 50, pp. 3296-3307, 2008.
[6] B. Beckhoff, Handbook of practical X-ray fluorescence analysis. Berlin;
London: Springer, 2006.
[7] R. v. Grieken and A. A. Markowicz, Handbook of X-ray spectrometry, 2nd
ed., rev. and expanded. ed. New York, N.Y.: M. Dekker, 2002.
[8] J. C. Drury, Ultrasonic flaw detection for technicians, 3rd ed. [Swansea]:
Silverwing Ltd., 2004.
[9] R. Baboian, Corrosion tests and standards : application and interpretation.
Philadelphia, Pa.: ASTM, 1995.
[10] H. H. Uhlig and R. W. Revie, Corrosion and corrosion control : an
introduction to corrosion science and engineering, 4th ed. / R. Winston
Revie. ed. Hoboken, N.J.: Wiley-Interscience; Chichester: John Wiley
[distributor], 2008.
[11] R. C. Bill, "The role of oxidation in the fretting wear process," 1981.
[12] A. Neyman and O. Olszewski, "Research on fretting wear dependence of
hardness ratio and friction coefficient of fretted couple," Wear, vol. 162164, pp. 939-943, 1993.
[13] R. P. M. Procter, et al., "Stress-corrosion cracking of C---Mn steels in
methanol-ammonia environments--I. Effects of environmental and
mechanical variables," Corrosion Science, vol. 33, pp. 1009-1031, 1992.
[14] R. C. Newman, "Stress Corrosion Cracking," in Shreir's Corrosion, J. A. R.
Tony, Ed., Oxford: Elsevier, 2010, pp. 864-901.
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106 Materials Characterisation V


[15] C. A. e. Hampel, The encyclopedia of electrochemistry. NY: [s.n.], 1964.
[16] H. P. Hack, "Galvanic Corrosion," in Shreir's Corrosion, J. A. R. Tony,
Ed., Oxford: Elsevier, 2010, pp. 828-856.
[17] Z. Szklarska-Smialowska, Pitting corrosion of metals. Houston, Tex.:
National Association of Corrosion Engineers, 1986.
[18] R. Baboian, "Automotive corrosion tests and standards," 1996.
[19] M. F. Ashby and D. R. H. Jones, Engineering materials 2 : an introduction
to microstructures, processing and design, 3rd ed. Oxford: ButterworthHeinemann, 2006.
[20] F. F. Schmidt, The engineering properties of molybdenum and molybdenum
alloys. Columbus, Ohio: Defense Metals Information Center, 1963.
[21] P. Chamberlain and C. Ellis, British and American tanks of World War II:
the complete illustrated history of British, American, and Commonwealth
tanks, 1939-1945. London New York: Cassell & Co. ;Distributed in the
USA by Sterling Pub., 2000.
[22] R. Jackson, Tanks : and armoured fighting vehicles. Bath: Parragon, 2007.
[23] A. R. Mendoza and F. Corvo, "Outdoor and indoor atmospheric corrosion
of non-ferrous metals," Corrosion Science, vol. 42, pp. 1123-1147, 2000.
[24] I. Odnevall and C. Leygraf, "The formation of Zn4Cl2(OH)4SO4 5H2O
in an urban and an industrial atmosphere," Corrosion Science, vol. 36, pp.
1551-1559, 1994.

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Section 4
Computational models
and experiments

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Materials Characterisation V

109

A multi-factor interaction model (MFIM) for


damage initiation and progression
C. C. Chamis
NASA Glenn Research Center Cleveland, USA

Abstract
A Multi-Factor-Interaction-Model (MFIM) is briefly described to represent
complex point material behavior in a single equation. The model is of product
form in order to represent coupled interactions and to be computationally
effective. The model describes a continuum or surface in space that represents
the complex material behavior in terms of the various factors that affect a
specified material behavior. The material specified behavior is inclusive of all
material properties, mechanical, thermal, physical and effects thereon, such as
temperature, time, cyclic loadings, etc. Sample case results simulated by using
MFIM are compared with test data to illustrate its versatility and its relevance to
reality. These results show that the MFIM can accurately predict metal matrix
composite fatigue data and mechanical properties of a steel alloy. Helpful
guidelines for its effective use are also included.
Keywords: material properties, high temperature, nonlinearities.

1 Introduction
The simulation of complex material behavior resulting from the interaction of
several factors (such as temperature, nonlinear material due to high stress, time
dependence, fatigue, etc), has been mainly performed by factor-specific
representations. For example, entire text books are devoted to plasticity, creep,
fatigue and high strain rate to mention only a few. Investigators have derived
equations that describe material behavior for each factor-specific effect.
Suppose we visualize that the material behavior is a continuum represented by
some surface. Then, we can think of some representation which describes that
surface which is inclusive of all participating factors that affect material behavior
either singly or interactively in various combinations. To that end, research has
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110 Materials Characterisation V


been a continuing activity at Glenn Research Center for about twenty-five years.
It started with a primitive form of MFIM representation for describing complex
composite behavior in polymer matrix composites [1]. It was extended to metal
matrix composites [2] and continues to be evolved in Aerospace Plane and the
High Speed support of the National Research Programs. The result of all this
research is that general guidelines for its usage are briefly described. Simulation
results are presented and compared (where available) with experimental data to
illustrate its versatility and perhaps demonstrate the claim for its uniqueness.

2 Fundamental considerations and the (MFIM)


We start with the premise that if we are to quantify the range of factors affecting
material properties, we need a description of material behavior. In this context, it
is reasonable to consider that material behavior constitutes an n-dimensional
space (Material Behavior Space (MBS)) where each point represents a specific
aspect of material behavior. It is further reasonable to assume that MBS can be
described by an assumed interpolation function. One convenient interpolation
function is a polynomial of product form because mutual interactions among
different factors can be represented by the overall product, and includes those
cross products in common algebraic polynomials. In this investigation, MBS is
assumed to be described by the following multifactor interaction equation
(MFIM):
N
MP
Aimi
(1)
M P0
i 1
where M P is the property affected to be evaluated. MPo corresponds to the initial
(reference) material state or condition. Ai represents the ith factor that influences
material behavior, and mi is an exponent. Ai is further defined by:

B
(2)
Ai 1
B0
Here B represents a specific cause factor for behavior (for example,
temperature), and Bo is the corresponding final value. This concept is
schematically represented in Fig. 1, the development of the multi-factorinteraction model (MFIM) to represent complex material behavior by a single
equation. The objective of the present paper is to briefly describe MFIM and
present results obtained there from to illustrate its uniqueness and its versatility.
Values for Bo and mi for specific behavior are selected either from known
behavior or more likely from a best judgment in conjunction with consultations
with seasoned professionals for that behavior. By representing the MBS with the
MFIM of product form (Eq. (1)), we gain another distinct advantage. The
behavior factors, B, can also be represented by another level of MFIM or
progressive substructuring of equation (1). The progressive substructuring leads
to a multitier representation of the MBS that permits intrinsic lower tier
behaviors to influence more than one factor at the next higher tier. In other
words, the observed specific behavior (Bi may depend on another set of lower
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tier elemental behaviors). Further, the behavior factors in this lower set of
specific behaviors may depend on yet another next lower tier of elemental
behaviors. That is, there are usually sets and subsets of specific behaviors that
hierarchically influence the higher level behaviors. When this is done, N can be
limited to 6, (for example), but the number of factors influencing material
behavior at the next lower tier will increase exponentially as Nj where j is the
number of 6-factor tiers. For example, when j = 3, N = 216, and so forth. This
representation is natural for multiparallel processing computers where the tiers
are programmed with different granularities. Obviously, then, the motivation for
selecting such a form is for computational and programming effectiveness.
Another reason for selecting an MFIM of product form is that the effect of each
factor can be evaluated separately. The interpretation of Bo is that it represents a
scale, whereas mi represents a shape or path. For example, (1 B/Bo)mi where 1
> B/Bo and + < mi < , covers the whole space as is illustrated in Fig. 2.

Figure 1:

Conceptual schematic of material behaviour through a MultiFactor Interaction Model (MFIM).

The inclusiveness of this particular form, combined with its simplicity, makes
it very attractive for a computational simulation. An expanded form of MFIM is
shown in Eq. (3) below:
m

Mp Tgw T

Mpo Tgw To
E
...1 e
E
ef


1
Sf
Ce
1
Cef

t
1
Sf tf

...

Cc
1
Ccf

M NM
1
Sf Nf M

T NT
1

Sf Nf T


1
f

...

The Multifactor Equation

(3)

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112 Materials Characterisation V


for inclusiveness and convenience of presentation. The top line includes six
factors in parentheses: ( Tgw T) / (Tgw T0 ) denotes temperature effects: (1
/Sf ) denotes combined stress effect; (1 t / Sf tf ) denotes time dependent
effects: ( 1 m Nm / Sf Nfm ) denotes mechanical cyclic load effects where m is
the cyclic stress due to NM cycling; (1 T NT / Sf Nft ) denotes thermal stress
due to NT cycling; ( 1 / f ) denotes frequency effects due to frequency.
The factors in the second line denote erosion, corrosion and chemical or
metallurgical effects. The dots between the first and second lines indicate that
several other factors can be included. Suffice it to say that the MFIM is generic
and inclusive. Two points to be noted are: (1) not all terms have to be included;
and (2) substructuring may be appropriate after six factors. For example, the
three factors in the second line affect some, if not all the factors in the first line.
This definitely is the case for the chemical/metallurgical factor.

Figure 2:

Effect of variation in the exponent.

3 Guidelines for usage of the (MFIM)


Some general guidelines for usage of the MFIM are appropriate: (1) Several
factors may be programmed for inclusiveness. (2) Factors that do not contribute
to that simulation assign zero (0) exponents. (3) Selecting exponents may be
intriguing in the absence of data. Start with some guess of expected behavior
and let the feedback from the material property behavior to guide the next update. (4) The exponents can also be evaluated if there is some data available
especially from combined testing. This can be done by expressing the expanded
equation using logs and then evaluate them by using the least squares method
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since the exponents will be the coefficients of linear algebraic equations. (5) To
simulate block fatigue evaluate the degradation up to the end of the first block
then use the degraded properties for the second block and repeat for additional
blocks degradation after second input to third etc. (6) Unloading generally
requires different exponent then loading. Select the unloading exponent to
simulate the expected loading-unloading by stress cycle. (7) Intermittent time
effects are handled the same way as block fatigue. (8) Combined fatigue (thermo
mechanical) is simulated by using the corresponding cycles and stresses in the
respective factors. (9) Frequency effects are simulated in combination with
cyclic loads. Stress value is not needed here since it is included in the cyclic
effects factor. (10) The static stress and the temperature factors when present
are used in combination with all active factors for that simulation effect. (11) To
simulate fabrication process use the temperature factor, the stress factor due to
pressure, a flow model and update the geometry through the finite element model
of the component. The user will invent other ways to use MFIM that the author
has not even thought of yet.
The most important point to remember is that MFIM is to be used
incrementally where the current values are updated from global thermo
structural, etc. analyses. This may require a two level iteration: (a) local to
achieve local equilibrium. During the iteration, the factors are changed until
local equilibrium is reached; and (b) global to achieve global equilibrium with
respect to boundary loads and supports conditions and internal stress field or
energy input in the increment equals the energy added to the structure. Another
important point to note is that the exponent for specific factor in MFIM
represents a general trend and not the entire precise path from its reference value
to its final value. Also, note that the MFIM is used for all the properties that is
the same factors but with different exponent. Results from sample cases for
MFIM application are described for: metal matrix composites (MMC), and a
nickel base alloy. As mentioned previously, these results are presented to
illustrate a few of the generic features of the MFIM applicability to convey to the
reader what has be done and infer therefrom what can be done. The specific
how is described in the references.

4 MFIM application to MMC


In this sample case MFIM is part of the METCAN (Metal Matrix Composite
Analyzer) [3]. The simulation for the properties to be shown starts from the
fabrication process as depicted in Fig. 3.
The constituent material properties used are summarized in Table 1.
MMC Simulation of the transverse strength is shown in Fig. 4. For this
simulation the factors for temperature, stress, and time were activated with
respective exponents about 0.5. It can be observed that the simulation predictions
track the data almost exactly. That simulation is very complex because it
incorporates matrix, interphase and fibers. It starts from the fabrication process
and ends with monotonic loading to fracture. Sample simulation results for
fatigue of the same composite are compared with data in Fig. 5.
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114 Materials Characterisation V

Figure 3:
Table 1:

METCAN Metal Matrix Composite Behavior computational


simulation sequence.
Constituent (fiber/matrix) material properties used in METCAN.

It is observed that the agreement is very good. In addition, the simulation


identifies the types of failures that lead to specimen fracture that is achievable by
the use of the MFIM. For this case, the mechanical cycle term in the MFIM was
also activated with an exponent of about 0.5 for all the constituent properties.
Simulation results for stress at times are compared in Fig. 6. As can be seen the
agreement is very good.
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Figure 4:

Transverse stress strain curve of SiC/Ti-6-4 T = 73 oF, FVR = 0.34.

Figure 5:

Predicted isothermal fatigue life [0] SCS6/Ti-24A1-11 Nb, 0.35


FVR (70 oF (23 oC), R = 0.1).

Figure 6:

Creep behavior of [0] SCS6/Ti-24Al-11Nb composite at 815oC


and 310 MPa; FVR = 0.35; stress-free temperature = 815oC.

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116 Materials Characterisation V

Figure 7:

Calibration of nickel base alloy 713C elastic modulus as a function


of temperature.

Figure 8:

Calibration of nickel base alloy IN-100 coefficient of thermal


expansion as a function of temperature.

The time factor was activated for the fabrication process and the tensile load
to fracture. Additional simulation results are described in [3, 4].

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5 Properties for nickel base alloy


Simulation results of temperature effects on nickel base alloy 713C properties [5]
are shown respectively in Fig. 7 for modulus, Fig. 8 for thermal expansion
coefficient, Fig. 9 for thermal heat conductivity, and in Fig. 10 for heat capacity.
Collectively the comparisons are in good agreement.
Collectively these results show the effectiveness of MFIM.

Figure 9:

Calibration of nickel base alloy MAR-M 200 thermal conductivity


as a function of temperature.

Figure 10: Calibration of nickel base alloy IN-100 specific heat as a function of
temperature.
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118 Materials Characterisation V

6 Concluding remarks
The salient concluding remarks from a description of the multi-factor interaction
model (MFIM) to predict complex material behavior by using a single equation
and select applications are: (1) MFIM is a material point simulator. It is unique
and inclusive for both composites and metals. (2) It is used incrementally in
combination with analyses that provide local stress information. (3) It usually
requires alternative solutions consisting of both local and global convergence. (4)
Applications for meta matrix composites under different loading conditions
predicted results that were in very good agreement with test data. (5) Familiarity
and confidence and extensive usage will be gained by continuing usage
application to complex solutions of material behavior and to simulate difficult
and even untried problems.

References
[1] Chamis, C.C., Lark, R.F. and Sinclair, J.H.: Integrated theory for Predicting
the Hydrothermal Mechanical Behavior of Composite Structural
Components. ASTM pp. 160-192.
[2] Chamis, C.C. and Hopkins, D.A.: Thermo Viscoplastic Nonlinear
Constitutive Relationships Structural Analysis of High Temperature Metal
Matrix Component. NASA TM 87291, 1985
[3] Chamis, C.C., Murthy, P.L.N. and Hopkins, D.A.: Computational
Simulation of High Temperature Metal Matrix Composites Cyclic Behavior.
ASTM, STP 1080, 1990, pp 5669.
[4] Tong, M.T., Singhal, S.N., Chamis, C.C. and Murthy, P.L.N.: Simulation of
Fatigue Behavior of High Temperature Metal Matrix Composites. ASTM
Reprint from Standard Technical Publication, 1253, 1996, pp. 540-551.
[5] Boyce, L. and Chamis, C.C.: Probabilistic Constitutive Relationships for
Cyclic Material Strength Models. AIAA.ASME/ASCE/AHS 29th Structures,
Structural Dynamics and Materials Conference. Part 3, AIAA, 1988,
pp. 1299-1306.
[6] Progressive Fracture Structural Analysis of National Wind Tunnel
Structures by L. Minnetyan, NASA CR 198485, May 1996.

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Analytical solution of a two-dimensional


elastostatic problem of functionally graded
materials via the Airy stress function
H. Sakurai
Co-operative Education Centre,
Sendai National College of Technology, Japan

Abstract
Functionally Graded Materials (FGMs) possess properties that vary gradually as
a function of spatial coordinates. They are different from conventional composite
materials in that they have no distinct interfaces at which their material
properties change abruptly. These FGMs are suitable for various applications,
such as aerospace, nuclear fusion, biomaterial electronics, etc. In practice,
applications of analytical solutions are limited. However, the analytical solutions
are very important as standards for evaluating numerical simulation results and
they are also important to mathematical understanding. Little research on the
analytical solutions of two-dimensional elastostatic problems has been reported.
Furthermore, few analytical solutions using Airy stress functions have been
published. The purpose of this paper is to propose an analytical method for the
two-dimensional elastostatic problems of FGMs using the Airy stress function.
In the present investigation, FGMs in which the properties of the materials vary
exponentially in one direction are examined. A few numerical examples are
presented and the validity of the method is shown by comparisons with the
results of past studies.
Keywords: analytical solution, functionally graded material, two-dimensional
problem, Airy stress function.

1 Introduction
The Functionally Graded Materials (FGMs) possess properties that vary
gradually as a function of spatial coordinates. They are different from
conventional composite materials in that they have no distinct interfaces at which
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120 Materials Characterisation V


their material properties change abruptly [1]. These FGMs are suitable for
various applications, such as aerospace, nuclear fusion, biomaterial electronics,
etc. Chakraborty et al. developed a new beam element solving FGM beam
structures based on the first order shear deformation theory [2]. Nguyen et al.
proposed a first-order shear deformation plates models for modeling structures
made of FGMs [3]. Xinag and Yang studied free and forced vibrations of a
laminated FGM Timoshenko beam with variable thickness under heat
conduction [4]. Sankar and his co-workers have been reporting analytical
methods for the thermomechanical analysis of FGM beams [57].
Zhu and Sankar presented an elasticity solution of a simply supported FGM
beam having variation of Youngs modulus distributed by a polynomial in the
thickness direction [6]. In Ref. [6], the Fourier series method is used to reduce
the governing partial differential equations to the ordinary equations that are then
solved by the Galerkin method. Miers and Telles proposed the Boundary
Element-Free Method belonging to a meshless technique, for two-dimensional
elastostatic analysis of FGMs [8]. Zhong and Yu presented explicit solutions of a
cantilever FGM beam having arbitrary graded variations of material properties
distributed in the thickness direction based on two-dimensional theory of
elasticity [9].
Applications of analytical solutions are limited to practical shapes of analysis
regions and boundary conditions. However, the analytical solutions are very
important as standards for evaluating numerical simulation results, such as finite
element method etc., and they are also important to mathematical understanding.
Little research on the analytical solutions of two-dimensional elastostatic
problems has been reported. Furthermore, to the best of the authors knowledge,
few analytical solutions using Airy stress functions have been published.
The objective of the present paper is to describe the analysis of the twodimensional elastostatic problems of FGMs using the Airy stress function. In this
study, FGMs in which the properties of the materials change exponentially in
one direction are treated. A few numerical examples are presented and the
validity of the method is shown by the comparisons with the results of the
present method and results of past studies.

2 Two-dimensional problem of FGMs and basic equations


In the Cartesian coordinate system O-xz , we consider a simply supported FGM
beam subjected to a transverse load as shown in Fig. 1. The length in the x
direction is l and the length in the z direction is h . In Fig. 1, the uniform
transverse load and the simply supported boundary condition are one of the
examples.
In the absence of body forces the equilibrium equations are given as

xz zz

0
x
z
where xx , zz , zx are stress components and zx xz .
xx zx
0

z
x

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Materials Characterisation V

121

p z ( x) p 0

h
l

z
Figure 1:

An example of a simply supported FGM beam.

The relationships between strains and displacements are

xx
where

u
x

xx , zz , zx are

zz

w
z

zx

strain components and

u w

z x

(2)

u, w are the displacement

components in the x and the z direction respectively. The strain components


should also satisfy the following compatibility condition.

2 xx 2 zz 2 zx

0
zx
z 2
x 2

(3)

The constitutive equations are given as

xx s11 xx s13 zz
where

zz s13 xx s33 zz

zx s44 zx

(4)

s11 , s13 , s33 , s 44 are elastic moduli. The material properties of FGMs

change gradually as a function of spatial coordinates. We assume material


properties varying exponentially in the z direction, i.e.
z

s ij s F ( z ) s e h

(5)

where sij are their corresponding values in the plane

z z 0 with F(z0 )=1 and

0
ij

0
ij

F(z) , is called graded function, which expresses the distribution of material


properties, and the parameter is called the graded index [9]. Now, we
introduce Airy stress function ( x,z ) expressed by the following equations.

xx

2
2
z

zz

x 2

zx

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122 Materials Characterisation V


Substituting Eqns. (4)-(6) into Eqn. (3), the next governing equation with respect
to Airy stress function ( x , z ) is obtained.
4
3
4
4
0
0
0
0
s
s
s
s

(
2
)
2
13
44
33
11
h z 3
z 4
x 2 z 2
x 4
2
2
3
2
2
0
0
0
s
s
(2 s130 s 44
)

0
11
13
h x 2 z
h 2 z 2
h 2 x 2

s110

(7)

The above equation is the same form as the governing equation of the plates
bending with variable rigidity, and it is possible to adopt the same method for the
solution [10].

3 Method of solution
In Eqn. (7), we introduce the following Airy stress function ( x,z ) .

( x, z ) Ai ( z ) f i ( x)

(8)

i 1

The function f i ( x) should be assumed to satisfy the mechanical boundary


conditions at the x 0 and x=l . For instance, under the simply supported
condition and the cantilever condition, it should be chosen to satisfy xx=0, zz=0
at the both ends and xx=0 and xz=0 at the free end respectively.
3.1 Formulation for simply supported FGM beam subjected to uniform
pressure
In this problem, we assume the following function

Ai ( z ) f si ( x )
i 1

where

A ( z ) sin x

i 1, 3, 5

(9)

i
, f si ( x) sin i x . And the stress components are as follows
l

d 2 Ai ( z )
xx
f si ( x)
dz 2
i 1, 3, 5

zz

i 1, 3, 5

zx

i 1, 3, 5

2
i

Ai ( z ) f si ( x )

dAi
f ci ( x)
dz

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Materials Characterisation V

123

f ci ( x) cos i x . Substituting Eqn. (9) into Eqn. (7), the following


ordinary differential equation with respect to the unknown function Ai (z ) is
where

obtained easily.
3
2
2
d 4 Ai
2 d Ai
0 d Ai
0
0
0
s
s
s
s

(
2

}
11
11
13
44
i
h dz 3
dz 4
h2
dz 2
2
2 dAi
0
0
(2 s130 s 44
) i
( s33
i 2 s130 2 ) i 2 Ai 0
h dz
h

s110

(11)

The solution of the above equation is given as

Ai ( z ) C i ,1e i ,1 C i , 2 e i , 2 C i ,3 e i , 3 C i , 4 e i , 4
r z

where the

r z

r z

r z

(12)

ri , j ( j 1, 2, 3, 4) are the roots of the following the 4-th order

equation and the

C i , j ( j 1, 2, 3, 4) are arbitrary constants to be determined by

the boundary conditions at z h 2 and z h 2 .

2
2
1
3
0
) i2 ri , j
ri , j 2 0 (2 s130 s 44
h
s11
h

1 0 2
2
0
0 (2 s130 s 44
) i2 ri , j 0 ( s 33
i s130 2 ) i2 0
h
s11
s11
h

ri , j 2
4

Considering Fourier expansion of the transverse pressure

(13)

p z ( x) p0 , the

following equation is obtained.

pz

4 p0 1
1
f si ( x)
sin i x
i 1,3,5 i
i 1,3,5 i

4 p0

(14)

The boundary conditions at the both surfaces are as follows.


zz p0 , zx 0 at z h 2

zz 0

zx 0

at z h 2

(15)

Substituting Eqn. (10) and Eqn. (14) into Eqn. (15), the following four equations
for determining the arbitrary constants C i , j are derived.

4 p0
h
Ai ( )
2
i 2 i
h
Ai ( ) 0
2

dAi h
( ) 0
dz
2
dAi h
( )0
dz 2

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124 Materials Characterisation V

3.2 Formulation for cantilever FGM beam subjected to uniform pressure


We deal with the formulation of a cantilever FGM beam such as shown in Fig. 2.

p z ( x) p0

h
l

z
Figure 2:

An example of a cantilever FGM beam.

It is necessary to assume the function f i ( x) satisfying the mechanical


boundary conditions at the free end. One of the simplest functions satisfying the
above conditions is

A2 ( z ) f 2 ( x) A2 ( z ) x 2
where

(17)

f 2 ( x) x 2 . The stress components are as follows.

xx
zz
zx

d 2 A2 2
2 d 2 A2

f
(
x
)

x
2
z 2
dz 2
dz 2

d 2 f 2 ( x)
2

A
(
z
)

A2 ( z ) 2
2
x 2
dx 2

dA ( z ) df 2 ( x)
dA ( z )
2
2

2
2x
zx
dz
dx
dz

(18)

Substituting Eqn. (17) into Eqn. (7), the following ordinary differential
equation is derived again.
3
2
2
d 4 A2
0 2 d A2
0
0
0
2 d A2
s x
2s11 x
{2(2s13 s44 ) s11 2 x } 2
h
dz 4
dz 3
h
dz (19)
2

0 dA2
2(2s130 s44
)
2s130 2 A2 0
h dz
h
0 2
11

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Materials Characterisation V

125

We consider the above equation as the following ordinary differential


equation with respect to z at the given section x x0 (constant).
3
2
2
d 4 A2
2 d A2
2 d A2
0
0
0
0
s x
2s11 x0
{2(2s13 s44 ) s11 2 x0 } 2
h
dz 4
dz3
h
dz (20)
2

0 dA2
2(2s130 s44
)
2s130 2 A2 0
h dz
h
2
0
11 0

The solution of the ordinary differential equation is given in the same form as
Eqn. (12). The boundary conditions on the top z h 2 and on the bottom

z h 2 at the x x0 (constant) are expressed as follows.

h
A2 ( ) 2 p 0
2
h
A2 ( ) 0
2

dA2 h
( ) 0
dz
2
dA2 h
( )0
dz 2

(21)

4 Numerical examples
4.1 Analysis of simply supported FGM beam under sinusoidal pressure
Let us consider a simply supported FGM beam subjected to a sinusoidal pressure
as shown in Fig. 3. For convenience, the results are indicated in the coordinate
system of Fig. 3 [6]. The Youngs modulus is assumed to be of the form
E E0 e z h and the constitutive equation is the same as that of Ref. [7].

h
l

z
Figure 3:

A simply supported FGM beam subjected to sinusoidal pressure.

Two types of the material properties are considered, and the ratios of Youngs
moduli of the top surface and the bottom surface are Eh E0 =10 and

Eh E0 =0.1. In the case of the former, the graded index in Eqn. (5)
corresponds to 2.30 , and in the case of the latter, it corresponds to
=-2.30 . Further, in the case of the former, the load is applied on the softer
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126 Materials Characterisation V


surface and in the case of the latter, on the harder surface. In both cases, Youngs
modulus is E0 =1 [Gpa], Poissons ratio is 0.25 and the thickness is h 10
[mm].
The
type
of
the
applying
force
is
sinusoidal
pz ( x) p0 sin x=p0 sin ix l , =i l , i=1,3,5 .
Figure 4 shows the axial stress distribution at the middle span for
Eh E0 =10 ,h=1 , and Fig. 5 shows the shear stress distribution at the middle
span for Eh E0 =0.1 ,h=3 . In the figures, Galerkin method indicates the
results of Ref. [6]. The vertical axis is the normalized stress values. The stress
xx is divided by the xx ( x, h) , and the stress xz is divided by the average
value at the middle section. From these results, it can be noted that the present
results agree well with the results by Ref. [6] for the various conditions of the
analysis. Analysis of cantilever FGM beam under uniform pressure
The analysis of the cantilever FGM beam subjected to the uniform pressure as
shown in Fig. 2 have been carried out [9]. The length l is l = 1 [m] and the
thickness h is h = 0.2 [m]. The material properties at z = z0 = 0 are given Table 1,
and the magnitude of the transverse pressure p0 is p0 = 1 [Pa].
h=1, graded index=+2.30
Present solution

Galerkin method

xx(x,z)/xx(x,h)

2.0
0.0
0.0

0.2

0.4

0.6

0.8

1.0

-2.0
-4.0
-6.0
z/h

Figure 4:

Axial stress

xx ( x, z ) / xx ( x, h)

through the thickness of FGM

beam at x l 2 .
For the graded index
component

xx

3 ,

Fig. 6 shows the distributions of the stress

at the clamped edge. The horizontal axis is the non-dimensional

coordinate z and the vertical axis is the stress values. In this figure, Ref. [9]
means the results of Ref. [9]. The present results again are in good agreement
with those of Ref. [9]. It was also confirmed that the distributions of the stress
components zz and zx are also in good agreement.
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Materials Characterisation V

127

h=3 , graded index=-2.30


Present solution

Galerkin method

xz/xz(average)

2.0
1.5
1.0
0.5
0.0
-0.5 0

0.2

0.4

0.6

0.8

z/h

Figure 5:

Shear stress

xz / xz (average)

through the thickness of FGM

beam at x l 2 .
Table 1:

Materials properties.

Material constants

Values [1/Pa]

5.41 10 12

1.51 10 12

0
11
0
13

0
s33

9.52 10 11

0
s44

1.37 10 10
graded index =+3, -3

xx(l, z)

Present (=+3)
Present (=-3)

Ref.[9] (=+3)
Ref.[9] (=-3)

250.0
200.0
150.0
100.0
50.0
0.0
-50.0 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1
-100.0
-150.0
-200.0
-250.0
z/h

Figure 6:

Stress at the clamped end

0.2

0.3

0.4

0.5

xx (l , z ) ( 3 ).

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128 Materials Characterisation V


4.2 Analysis of simply supported FGM beam under uniform pressure
The simply supported FGM beam as shown in Fig. 1 is analyzed. The sizes, the
elastic constants and the applied load are the same as those of the previous
section. The graded index is assumed as 3 . The distributions of the stress
components xx at the x l 2 0.5 and zx at the x 0 are plotted in Figs. 7
8. The number of terms adopted in the Fourier series of Eqns. (9) and (14) is ten.
We confirmed that taking at least eight terms is sufficient accuracy for the
solution in this problem.
graded index =+3.0
20.0
10.0

xx

0.0
-10.0 -0.5 -0.4 -0.3 -0.2 -0.1

0.0

0.1

0.2

0.3

0.4

0.5

-20.0
-30.0
-40.0
-50.0
-60.0
-70.0
z/h

Figure 7:

Stress xx through the thickness at x 0.5.


graded index =+3.0

5.0
4.5
4.0

zx

3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5

-0.3

-0.1

0.1

0.3

z/h

Figure 8:

Stress zx through the thickness at x 0 .

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0.5

Materials Characterisation V

From these results, the value of the stress value


stress zx . Comparing the tensile stress
compressive stress

xx

xx

xx

129

is greater than that of the

on the bottom surface with the

on the top surface, the greater compressive stress is

caused on the softer surface. The shear stress distribution

zx

is different from

that for homogeneous beams. The point where the maximum stress appears
moves toward the softer surface. It may be possible to control distribution of
stresses by adjustment of materials properties.

5 Concluding remarks
In this paper, one analytical solution method for two-dimensional elastostatic
problems in FGMs in which the properties of the materials vary exponentially in
one direction is proposed. The method is based on the idea that the governing
equation of this problem is of the same form as the governing equation for the
plate bending with variable rigidity. The analysis method uses the Airy stress
function. From analysis of a few numerical examples, most of the results
correlate well with other solutions and the validity of the method is shown. The
distributions of displacement components are not stated, however we can obtain
them by integrating the strains and displacements relationships.
Future work will be focused on development of an analytical method of
solution for analyzing problems of FGMs having an arbitrary variation of their
material properties expressed by functions other than exponential.

References
[1] Suresh, S., and Moretensen, A., Fundamentals of Functionally Graded
Materials, IOM Communications Ltd, London, 1998.
[2] Chakraborty A., Gopalakrishnan S. and Reddy JN., A new beam finite
element for the analysis of functionally graded materials, International
Journal of Mechanical Science, Vol.45, pp.519-539, 2003.
[3] Trung-Kien Nguyen, Karam Sab and Guy Bonnet, First-order shear
deformation plate models for functionally graded materials, Composite
Structures, 83, pp.25-36, 2008.
[4] H.J. Xinag and J. Yang, Free and forced vibration of a laminated FGM
Timoshenko beam of variable thickness under heat conduction,
Composites: Part B Vol.39, pp.292-303, 2008.
[5] Sankar BV., An elasticity solution for functionally graded beams,
Composite Science Technology, 61, pp.689-696, 2001.
[6] Zhu H. and Sankar BV., A combined Fourier series-Galerkin method for
the analysis of functionally graded beams, Journal of Applied Mechanics,
Vol.71, pp.421-424, 2004.

WIT Transactions on Engineering Sciences, Vol 72, 2011 WIT Press


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130 Materials Characterisation V


[7] Sankar BV. and Tzeng JT., Thermal stresses in functionally graded beams,
AIAA Journal, Vol.40, pp.1228-1232, 2002.
[8] L.S. Miers and J.C.F. Telles, Two-dimensional elastostatic analysis of
FGMs via BEFM, Engineering Analysis with Boundary Elements, Vol.32,
pp.1006-1011, 2008.
[9] Zheng Zhong and Tao Yu, Analytical solution of a cantilever functionally
graded beam, Composite Science and Technology, Vol.67, pp.481-488,
2007.
[10] Mansfield, E.H., The Bending and Stretching of Plates, Pergamon Press,
pp.64-73, 1964.

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Materials Characterisation V

131

Moment curvature analysis of concrete flexural


members confined with CFRP grids
A. Michael & P. Christou
Department of Civil Engineering, Frederick University, Cyprus

Abstract
The moment-curvature (M-) diagrams define the maximum capacity of
structural elements that are primarily subjected to bending moments and
therefore their failure mode is flexural. The moment-curvature diagrams are also
used to assess the ductility of structural elements and are therefore very
important for the determination of the amount of plastic energy a structural
element can absorb. One way of improving the reinforced concrete (RC)
members is the confinement of concrete with FRP composites. The work
presented in this paper includes the development of moment curvature diagrams
for RC members using a fiber model. The RC members were designed as
compression controlled members meaning that their failure initiates in the
concrete prior to yielding of the steel tension reinforcement. These types of
members have limited ductility. The introduction of a specific amount of Carbon
Fibre Reinforced Polymer (CFRP) composite grid as confining reinforcement
improves the ductility of the RC members by as much as 30%. The results from
the fiber model are compared to available results from an experimental program
conducted to evaluate the experimental improvement of the ductility of
compression controlled members. The experimental and analytical results are a
good match indicating that the fiber model is accurate and can be used to develop
the moment-curvature diagrams of RC members confined with a CFRP
composite grid.
Keywords: CFRP grid, concrete confinement, moment curvature, ductility.

1 Introduction
Compression controlled steel reinforced members, fail through crushing of
concrete and therefore lack the ductility that is associated with yielding of the
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132 Materials Characterisation V


reinforcement. This is due to the fact that concrete as a material does not behave
in a ductile manner. Concrete may exhibit limited ductility (also called pseudo
ductility) but this ductility varies depending on the aggregate material and the
strength of concrete used. High strength concrete is more brittle than low
strength concrete and therefore for high strength concrete the pseudo ductility
diminishes. This is similar to concrete members reinforced with Fibre Reinforced
Polymer (FRP) composites. FRP reinforcing bars when loaded in tension, exhibit
linear stress-strain behaviour up to rupture. There is no yield point and associated
plateau to provide a ductile response when used as tensile reinforcement in
concrete. Rooney and Taylor [1], Toutanji and Deng [2], and Grace et al. [3]
found that the post cracking beam behaviour was linear to failure in concrete
beams reinforced with glass FRP rods which shows the lack of a yield plateau
and therefore the lack of a ductile response. There have been attempts to improve
the ductility of FRP with little or no success. If these members are designed in
such a way in order to fail through concrete crushing limited ductility may be
exhibited much like in the case of compression controlled members.
Therefore, the focus of improving member ductility should be on the concrete
for compression controlled members. If the concrete in the compression zone of
a flexure dominated member is confined then degradation of the compression
zone at capacity is delayed, resulting in a more ductile response.
Carbon Fibre Reinforced Polymer (CFRP) composite grids have been used to
reinforce concrete decks and beams for both strength and crack control [48]. The
CFRP composite grid has been used as confinement reinforcement with promising
results. In a series of cylinder tests conducted by Michael et al. [9] it was found
that the crushing strain of CFRP composite grid confined concrete was more than 2
times higher than the crushing strain of unconfined concrete.
The advantage that the CFRP composite grid has over the use of FRP
composite wraps that have been used for both confinement of concrete or
strengthening of concrete members is the ability of the CFRP composite grid to
be embedded in the concrete. The CFRP composite grid has openings that allow
concrete to flow through thus can be embedded in the member during
construction. This also provides environmental protection to the CFRP
composite since the composite is not exposed to the natural elements that can
cause environmental degradation to the FRP composite.
Moment-curvature diagrams are used to assess the ductility of structural
elements and are therefore very important for the determination of the amount of
plastic energy a structural element can absorb. The research presented in this
paper evaluated the moment-curvature response of compression controlled RC
members confined with CFRP composite grid with the use of a fiber model that
plots the moment-curvature diagram of such sections.

2 Experimental investigation
The unique application of the CFRP composite grid as confining reinforcement
was evaluated with the construction of two beams. Beam 1 had no CFRP
composite grid tubes and served as the control beam and beam 2 had two CFRP
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Materials Characterisation V

133

composite grid tubes placed in the compression zone. Details of the dimensions,
amount and location of steel reinforcement and CFRP composite grid tubes are
provided in Figures 1 and 2. The CFRP composite grid was formed into a
circular tube using a 152 mm diameter plastic pipe and was held in place by a
thin rope wrapped around the tube along its length.
5 in (127 mm)

3 in (76 mm)

2.75 in
(70 mm)
18 in
(457 mm)
6.65 ft (2.03 m)

2.7 ft (0.81 m)

6.65 ft (2.03 m)

16 ft (4.87 m)
1 in (25 mm)

1 in (25 mm)

#3 (#10) Stirrups

18 in (457 mm)
8 #10 (#32) Bars
2.75 in (70 mm)

2 in (51 mm)

3 in (76 mm)
12 in (305 mm)

Figure 1:
5 in (127 mm)

Details of control beam.


13 ft (3.96 m)

2.75 in
(70 mm)
18 in
(457 mm)
6.65 ft (2.03 m)

2.7 ft (0.81 m)

6.65 ft (2.03 m)

16 ft (4.87 m)
0.75 in (19 mm)

1 in (25 mm)
1 in (25 mm)

6 in
(152 mm)

#3 (#10) Stirrups

18 in (457 mm)
8 #10 (#32) Bars
2.75 in (70 mm)

2 in (51 mm)

3 in (76 mm)
12 in (305 mm)

Figure 2:

Details of grid beam.

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134 Materials Characterisation V


The beams were tested in a simply supported four-point bending
configuration (see Figure 3) in displacement control mode, that is, a constant
displacement rate was applied independently of the amount of load. The span
length between the two supports was 4.27 m, whereas the total length of the
beams was 4.87 m.
Actuator 1
Load Cell

Spreader Beam
D15

D14

D13

D12

D11

D10

D9

D8

D7

D6

D5

D4

D3

D2

D1

18 in
(457 mm)

1 ft (305 mm) Typ.

North
Support

South
Support
5.5 ft (1.7 m)

LVDT

3 ft (0.91 m)

Tilt Meter

Figure 3:

5.5 ft (1.7 m)

60 mm Foil Gauge

Test set-up.

3 Moment curvature analysis


The moment-curvature (M-) diagrams of the beams were calculated based on
experimental data and also based on a theoretical fiber model.
The experimental moment-curvature diagrams were calculated based on the
displacement profile curves at increasing loads. The displacement profile
equation was generated by fitting a 3rd order polynomial line to the displacement
profile curves. The fitted lines were in good agreement with the displacement
data (average R2 = 0.99). The polynomial displacement profile equation of the
beam was used to determine the curvature at specific points along the length of
the beam. The second derivative of the polynomial displacement profile equation
is the curvature equation.
The M- curves of the beams were calculated using a fiber model. The
compression zone of the tube beam was separated into two regions with regard to
concrete properties. The first region was the concrete cover on top of the CFRP
grid tubes and the second region was from the neutral axis to the top of the
CFRP grid tubes (see Figure 4). The first region was extended approximately
0.25 in. (6.5 mm) below the top of the CFRP grid tubes to account for the
unconfined concrete at the sides and between the grid tubes. The first region was
assigned unconfined concrete properties and the second region confined
properties. The concrete area from the neutral axis to the bottom of the grid tubes
was unconfined but was treated as confined concrete for simplicity and because
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Materials Characterisation V

135

the strains in that area close to the neutral axis were small and therefore the
effect on the strength was minor. The unconfined region was divided into one
rectangular layer while the confined region was divided into eight rectangular
layers. For the control beam, the compression zone was treated as an unconfined
concrete region and was divided into eight layers.
1 in. (25 mm)

c - 25 mm
(c - 1 in.)

0.75 in. (19 mm)

Grid Tube
N. A.

Unconfined concrete
Confined concrete

Figure 4:

Tube beam cross-section fiber model.

Some of the assumptions employed in this fiber model include perfect bond
between concrete and the reinforcing bars (strain compatibility), plain sections
remain plain (linear strain distribution), the area below the neutral axis was
considered cracked and was ignored in the force and moment calculation and
monotonic loading and deformation of the section.
The compressive force in each layer was calculated as the product of the area
of the layer and the average stress. The average stress was determined based on
the strain in the layer and the stress-strain curves of concrete. The Hognestad
parabola was used to calculate the stress-strain curve of unconfined concrete.
The modified Hognestad was used to calculate the stress-strain curve of confined
concrete [10]. The parameters of the modified Hognestad were determined based
on the available data from confined concrete cylinder tests [9].
The tensile force was calculated as the product of the area of steel
reinforcement and the steel stress. Steel stress was determined based on the
average strain of the two steel layers and by assuming elastic perfectly plastic
stress-strain curve.
The moment in the cross-section for the applied curvature distribution was
determined by summing moments about the neutral axis.
The moment curvature diagram was calculated by applying increasingly
larger top concrete compressive strains (c) to the cross-section and varying the
location of the neutral axis (c) until equilibrium of the axial forces (zero) in the
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136 Materials Characterisation V


cross-section for the applied strain was achieved. The curvature of the section (
= c / c) was then calculated based on the concrete compressive strain and the
location of the neutral axis.
The experimental and fiber model M- diagrams were calculated for both
beams. The theoretical and fiber model M- diagrams for the control beam (see
Figure 5) were approximately the same.
The fiber model M- behaviour of the tube beam was comparable to the
experimental behaviour (see Figure 6). The improvement in the ductility of the
Curvature x 1000 (rads/m)
16
24
31

39

500

678

400

542

300

407

200

271
Experimental
Fiber Model

100

136

0
0

0.2

0.4
0.6
0.8
Curvature x 1000 (rads/in)

Figure 5:

Moment (kip-ft)

Moment (kN-m)

M- curves for control beam.

Curvature x 1000 (rads/m)


16
24
31

39

500

678

400

542

300

407

200

271

Expiremental
Fiber Model

100

136

0.2
0.4
0.6
0.8
Curvature x 1000 (rads/in)

Figure 6:

M- curves for tube beam.

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Moment (kN-m)

Moment (kip-ft)

Materials Characterisation V

137

tube beam compared to the control beam, although relatively small, was evident
when the experimental M- curves for both beams were compared (see Figure
7). The area under the load-displacement curve represents the amount of energy
a structure can absorb before failure. The amount of energy is also a good
indicator of ductility. Ductile structures usually can absorb higher amounts of
energy compared to non-ductile (brittle) structures.

Curvature x 1000 (rads/m)


16
24
31

39

500

678

400

542

300

407

200

271

Control
Grid

100

Moment (kN-m)

Moment (kip-ft)

136

0.2
0.4
0.6
0.8
Curvature x 1000 (rads/in)
Figure 7:

Experimental M- curves.

The areas under the experimental moment-curvature curves, of both beams,


were calculated and compared. The area under the load-displacement curve of
the tube beam was approximately 37% more than that of the control beam. The
energy up to peak load was elastic energy while the post peak energy was
inelastic. Therefore, the 37% extra energy was primarily inelastic energy which
indicated the ability of the tube beam to undergo inelastic deformation compared
to the control beam. This represents an improvement in the ductility of the
member and is due to the confining effect of the CFRP composite grid.
Another way to measure ductility is through ductility factors. Curvature
ductility factors are a good way to evaluate the ductility of RC members. The
curvature ductility factor () is defined as the ratio of the ultimate curvature
(u) over the curvature at first yield (y).
The definition of ultimate and yield curvatures is simple when the behaviour
is elasto-plastic. Definition of these parameters is more complicated when the
behaviour is not elasto-plastic. Usually the behaviour of reinforced concrete is
not perfectly elasto-plastic. Therefore, the need for a consistent definition of the
ultimate and yield curvatures was realized. Researchers have proposed
definitions of ultimate and yield displacement and curvature as well as
instructions on how to calculate them.
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138 Materials Characterisation V


The ultimate curvature has been defined as the curvature at which the lateral
load in the descending portion of the load-displacement curve is not less than
80% of the maximum load (Pu) [1114]. Park and Paulay [15] have argued that
the available ultimate deformation (and therefore curvature) is not necessarily the
deformation that corresponds to the maximum load capacity. They further argued
that when survival without collapse is the criterion, it is too conservative to
define ultimate deformation as the deformation corresponding to the maximum
load-carrying capacity. It would seem reasonable to recognize at least some of
this deformation capacity after the maximum load has been reached and to
define the available ultimate deformation as that deformation when the loadcarrying capacity has reduced by some arbitrary amount after maximum load.
For example, a 10 or 20% reduction in maximum load-carrying capacity could
be tolerated in many cases, but the exact amount would depend on the particular
case.
The yield displacement (and therefore curvature) can be defined as the
displacement at the intersection of the horizontal line representing the ideal
lateral capacity, Pi, (nominal capacity using the ACI 318 approach and a
reduction factor of unity) and the straight line that passes through zero and the
point in the load-displacement curve at 75% of the ideal lateral capacity [1113].
The definitions of yield and ultimate displacements are depicted in Figure 8.
P
Pu
Pi
0.8 Pu
0.75 Pi

Figure 8:

d y or d c

du

Ductility factor component definitions.

The curvature ductility () was approximately 1.5 and 2 for the control and
tube beam respectively. The schematic for determining u and c for the control
beam is shown in Figure 9. The same approach was used in determining the
ductility factor for the tube beam. The curvature ductility factor of the tube beam
was approximately 33% higher than the curvature ductility factor of the control
beam.
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Materials Characterisation V

Curvature x 1000 (rads/m)


16
24
31

39
678

400

Mu
Mi

542

300

0.8 Mu
0.75 Mi

407

200

271

100

136
c

0
0

Figure 9:

0.2

0.4
0.6
0.8
Curvature x 1000 (rads/in)

Moment (kN-m)

500

Moment (kip-ft)

139

0
1

Curvature ductility factor for control beam.

The curvature ductility factor using the fiber model moment-curvature


diagram of the control beam was approximately 1.6 which was approximately
4% higher than the experimental. On the other hand, the curvature ductility
factor of the tube beam was approximately 2.45 which was an overestimate of
approximately 21%.

4 Conclusions
In this paper the development of moment-curvature diagrams for compression
controlled RC sections confined with CFRP composite grids was presented.
These diagrams were compared with diagrams developed from experimental data
for the same sections. Based on the results from this comparison the following
conclusions can be drawn:
1. The results from the two beams indicate that the CFRP grid provided
confinement to the concrete. Confinement was achieved using a series
of small diameter CFRP grid tubes rather than wrapping the entire
cross-section.
2. The curvature ductility factor of the beam utilizing the CFRP grid tubes
was improved by 33% compared to the control beam with no grid tubes.
The improvement was significant, considering the small amount of
CFRP that was used to confine the compression zone.
3. The energy dissipation of the tube beam was 37% higher compared to
the controlled beam due to the effect of concrete confinement. This
increase in the energy dissipation of the element also represents an
improvement in the ductility due to concrete confinement from the
CFRP grid tubes.
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140 Materials Characterisation V


4.

5.

The results from the fiber model are fairly accurate compared to the
experimental data and therefore the model is considered valid.
However, there is a divergence after the peak load and further
refinement of the model is required.
The number of test specimens is limited and therefore the more testing
is required. Due to the small number of test specimens the conclusions
are drawn with great caution.

References
[1] Rooney, J., and Taylor, S., 2004, Flexural Behaviour of Steel and GFRP
Reinforced Concrete Beams, Composites: Part B, Vol. 27, No 3-4,
pp. 38-40.
[2] Toutanji, H., and Deng Y., 2003, Deflection and Crack Width Prediction
of Concrete Beams Reinforced with Glass FRP Rods, Construction and
Building Materials, Vol. 17, No 1, pp. 69-74.
[3] Grace, N. F., Soliman, A. K., Sayed, G. A., and Saleh, K. R., 1998,
Behavior and Ductility of Simple and Continuous FRP Reinforced
Beams, Journal of Composites for Construction, Vol. 2, No 4,
pp. 186-194.
[4] Rahman, A. H., Kingsley, C. Y., and Kobayashi, K., 2000, Service and
Ultimate Load Behavior of Bridge Deck Reinforced with Carbon FRP
Grid, Journal of Composites for Construction, Vol. 4, No 1, pp. 16-23.
[5] Yost, J. R., Goodspeed, C. H., and Schmeckpeper, E. R., 2001, Flexural
Performance of Concrete Beams Reinforced with FRP Grids, Journal of
Composites for Construction, Vol. 5, No 1, pp. 18-25.
[6] Harries, K. A., and Gassman, S. L., 2003, Load Tests of Reinforced
Concrete Catch Basing Knockout Panels, Department of Civil and
Environmental Engineering, University of South Carolina, Report No
ST03-01, p. 21.
[7] Shao, Y., Johnson, C., and Mirmiran, A., 2003, Control of Plastic
Shrinkage Cracking of Concrete with TechFab Carbon FRP Grids,
Department of Civil, Construction, and Environmental Engineering, North
Carolina State University, Report to Tech-Fab Inc, p.
[8] Hamilton, H. R, Cook, R. A., and Alfonzo, L., 2006, Crack Control in
Toppings for Precast Flat Slab Bridge Deck Construction, Department of
Civil and Coastal Engineering, University of Florida, Engineering and
Industrial Station, Final Report Submitted to FDOT, UF Project No
00030907, p. 120.
[9] Michael, A. P., Hamilton, H. R. III, and Ansley, M. H. (2005). Concrete
confinement using carbon fiber reinforced polymer grid, American
Concrete Institute, SP230-56, Vol. 230, pp. 991-1010.
[10] Park, R., and Paulay, T., 1975 (a), Chapter 6: Ultimate Deformation and
Ductility of Members with Flexure, Reinforced Concrete Structures, John
Wiley & Sons, New York, NY, pp. 195-269.

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Materials Characterisation V

141

[11] Priestley, M. J. N., and Park, R., 1987, Strength and Ductility of Concrete
Bridge Columns under Seismic Loading, ACI Structural Journal, Vol. 84,
No 1, pp. 61-76.
[12] Zahn, F. A., Park, R., and Priestley, M. J. N., 1990, Flexural Strength and
Ductility of Circular Hollow Reinforced Concrete Columns without
Confinement on Inside Face, ACI Structural Journal, Vol. 87, No 2,
pp. 156-166.
[13] Sheikh, S. A., and Khoury, S. S., 1993, Confined Concrete Columns with
Stubs, ACI Structural Journal, Vol. 90, No 4, pp. 414-431.
[14] Yeh, Y. K., Mo, Y. L., and Yang, C. Y., 2002, Seismic Performance of
Rectangular Hollow Bridge Columns, Journal of Structural Engineering,
Vol. 128, No 1, pp. 60-68.
[15] Park, R., and Paulay, T., 1975 (b), Chapter 11: Strength and Ductility of
Frames, Reinforced Concrete Structures, John Wiley & Sons, New York,
NY, pp. 496-609.

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Materials Characterisation V

143

Application of effective media theory in the


characterization of the hygrothermal
performance of masonry
Z. Pavlk, E. Vejmelkov, L. Fiala, M. Pavlkov & R. ern
Department of Materials Engineering and Chemistry,
Faculty of Civil Engineering, Czech Technical University in Prague,
Czech Republic

Abstract
Hygric and thermal properties of several types of materials which are used in
reconstructions of historical stone masonry on Czech territory are experimentally
measured at first. The obtained data are then subjected to a homogenization
procedure, and the effective heat and moisture transport and storage parameters
of the typical fragment of masonry are calculated. For the homogenization, a
mixing model originally derived for applications in dielectric studies was
employed taking into account the theoretical bounds of the investigated material
parameters. The obtained data can find use in damage assessment of historical
masonry using methods of computational simulations and analysis.
Keywords: hygric properties, thermal properties, historical stone masonry,
argillite, sandstone, lime-based plaster, homogenization techniques.

1 Introduction
The hygrothermal behaviour of climatically exposed components and structures
of historical buildings is related to the hygric, thermal, mechanical and other
physical and chemical properties of inbuilt materials. Their knowledge
represents necessary information for the understanding of the building
performance as well as the first step in avoiding damage, degradation or the
undue heat loss from the constructions.
The damage assessment of historical masonry and other structures due to the
negative effects of moisture and temperature can be done effectively by means of
mathematical and computational modelling. In this way, the time development of
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doi:10.2495/MC110131

144 Materials Characterisation V


moisture and temperature fields can be obtained which is a crucial for a proper
assessment of possible future damage [1]. Their prediction is a very important
task when preserving historical bridges and buildings or insulating existing
buildings and components. The moisture and temperature values can be then
assigned to the mechanical properties and to the risk of consequent damage. For
instance Charles Bridge in Prague, Czech Republic, which was subjected to
reconstruction works lately, is a typical example of extensive damage mostly
brought about by temperature and moisture impacts.
For the effective application of computational modelling in the buildings
performance analysis, there is necessary complete knowledge of material
properties of applied materials as well as of initial and boundary conditions of
simulations. As the initial conditions for the hygric and thermal analysis, the
moisture and temperature fields experimentally measured in the investigated
structure can be used. Boundary conditions of the computer simulations are
given by the climatic loading that can be simply adopted using meteorological
data.
In the technical practice, simplified calculations of building structures
behaviour are very often used. Here, in the computational simulations of heat
and moisture transport processes, brick or stone masonry is often understood as a
single material, the brick or stone itself. This simplification may work reasonably
well when the properties of the brick or stone and the mortar are similar.
However, this may not always be the case in some historical buildings, where
low-quality mortars were often used [2]. On that account, the results of such
calculations are diverse from the real state of the buildings, and cannot be
effectively used for estimation of some appropriate materials damage and
problems in hygrothermal behaviour. Therefore, solution of this problem must be
found in order to improve the accuracy and reliability of computational
modelling of building structures performance.
There are two ways how to meet the above given requirements on reliability
and accuracy of computational simulation of heat and moisture transport. The
first possibility is the use of sophisticated simulation tools that allow
discretization of studied structure in such resolution, that all the properties of
inbuilt materials can be assigned to the specific places of the structure. Although
this procedure is generally correct, it is too complex and sophisticated for wider
application in engineering practice, especially in case of conservationists of
historical buildings that are usually well oriented in materials problems without
knowledge of methods of computational modelling.
The second, and probably the most straightforward way to solve the problem
of differences in the properties of the particular components of masonry is the
utilization of the effective media theory. This procedure we introduce in the
presented work as an effective tool for simplification of computational modelling
of transport processes in the masonry. Application of homogenization principles
produces the macroscopic equations which may be used when analyzing the
masonry as a whole. In these equations, the effective parameters are used instead
of the parameters of the brick or stone.

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Materials Characterisation V

145

Quite apparently, the homogenization process cannot be done without the


exact knowledge of the properties of all materials constituting the masonry and
of the amount of each material in the analyzed wall. Therefore, the experimental
measurement of all the material parameters characterising the process of heat and
moisture transport and accumulation in inbuilt masonry materials is necessary at
first. These data are than implemented in the mixing models based on effective
media theory, and the effective thermal and hygric parameters of the whole
masonry can be calculated.

2 Studied materials
Two types of stones that were in the past often used in Czech region as bearing
masonry materials are analysed together with lime-based mortar with pozzolana
admixture.
Many historical buildings in the Czech Republic were built using similar
kinds of sandstone. Siliceous raw-grained sandstone was usually used for
historical architectural constructions (walls, portals, window frames) for its
strength. Ornamental parts of the architecture (gothic flowers, romantic shells)
and sculptures (from the Romanesque period up to now) were made of finegrained calcite-argillaceous sandstone. In this work, sandstone from Men-lzn
quarry, Czech Republic, is chosen. It is fine-grained psamitic equigranular rock,
about 95% of which is made up of suboval quartz clasts. Other mineral grains are
present only as minorities (tourmaline, epidote, muscovite and zircone). Quartz
grains reach up to 0.1 mm in diameter, but those of muscovite are larger, up to
0.3 mm [3]. The matrix is formed by clay minerals (mainly kaolinite).
Also the argillite was very popular material in historical architecture. It was
used for sacral as well as for secural buildings, flagstone pavements, roof slabs,
and facing. The studied argillite is coming from quarry Dbn, Czech Republic.
Its main constituents are illite, calcite, minerals on the basis of SiO2 having
granularity 0.3 0.15 mm, feldspar, and mica, whereas rigid materials form 40
60% of argillite volume.
Within the reconstruction of historical buildings, renewal and restoration of
interior and exterior plasters50and
mmortars is often done. From the point of view of
a historian, it is not acceptable to use lime-cement mortars in Romanesque,
Gothic, Renaissance, and Baroque buildings. However, the pure lime-based
plaster does not exhibit sufficient resistivity against moisture action. On that
account, proper hydraulic admixtures must be used that enhance the durability of
mortars. These materials must have similar composition as the historical
materials and they have to be applicable by the original technological processes.
As the chemical analyses of many plasters from historical buildings show, the
past centuries external plasters that are preserved until today contain products
formed by lime reaction with pozzolanic or hydraulic admixtures. Pozzolanic
admixtures appeared to have positive effect on properties of lime binder in the
past. On that account, lime-based mortar with metakaolin addition as pozzolana
admixture was chosen. The composition of the lime-metakaolin plaster was as

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146 Materials Characterisation V


follows: hydrated lime 400 g, metakaolin - 80 g, natural quartz sand with
continuous granulometry 0 to 2 mm 1 440 g, and water 480 g.

3 Experimental methods
Basic material properties of all tested materials were determined at first. Bulk
density and matrix density were measured using gravimetric method and helium
pycnometry, and then total open porosity was calculated. The samples
dimensions for these measurements were 40 x 40 x 20 mm.
For determination of water vapour transmission properties we applied cup
method, according to the European standard EN ISO 12571 [5]. The
measurements were carried out in steady state under isothermal conditions. We
used dry cup arrangement of the experiment. Here, the sealed cup with the
studied material sample containing burnt CaCl2 (0% relative humidity) was
placed in a controlled climatic chamber at 250.5C and 50% relative humidity
and it was weighed periodically. The circular samples had diameter 95 mm and
thickness of 20 mm. The steady state values of mass gain were utilized for the
determination of the water vapour permeability. On the basis of measured water
vapour permeability, the water vapour diffusion coefficient and water vapour
resistance factor were calculated using the simple formulas given in [6, 7].
For determination of moisture diffusivity as function of moisture, the
moisture profiles were measured at first. The measurements were done on
samples having dimensions of 40 x 20 x 300 mm in 1-D experimental
arrangement of water transport. The moisture content in specific position in
sample was measured by capacitance technique calibrated by gravimetric
method. The moisture dependent moisture diffusivity was then calculated using
inverse analysis of measured moisture profiles by means of Boltzmann-Matano
treatment [8].
In the sorption isotherm measurement, the samples were placed into the
desiccators with different salt solutions to simulate different values of relative
humidity. The mass of samples was measured in specified periods of time until
steady state value of mass was achieved. Then, the volumetric moisture content
was calculated and sorption isotherm of each tested material was plotted.
The thermal conductivity as the main parameter of heat transport was
determined using the commercial device ISOMET 2104 (Applied Precision,
Ltd.). ISOMET 2104 is a multifunctional instrument for measuring thermophysical parameters which is based on the application of an impulse technique
and is equipped with various types of optional probes. Thermal conductivity was
measured in the moisture range from the dry state to full water saturation on the
70 mm cubes.

4 Effective media theory and homogenization techniques


Application of effective media theory allows determination of the properties of
the whole masonry or building structure instead of parameters of the particular
inbuilt materials. In terms of effective media theory, the final composite structure
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Materials Characterisation V

147

(in our case stone masonry wall) can be considered basically as a mixture of
walling blocks and mortar. In more precise calculations, each of these materials
can be further considered as a mixture of three phases, namely solid, liquid and
gaseous phase (in four phase systems, the effect of bound water can be included)
that form their matrix and porous space. There are two basic approaches that can
be applied for determination of thermal and hygric properties of the stone
masonry. The first possibility is to apply homogenization techniques on the
moisture dependent material data of the materials involved in the masonry. This
simplified procedure was used in this work. The second possibility is based on
the complete knowledge of material properties of the particular components
forming the porous body of the structure (dry stone, dry mortar, free water,
bound water and air). From the properties of particular components and their
volumetric fractions the effective properties of the stone masonry can be
accessed.
On the basis of previous experience with application of homogenization
techniques, we have chosen for the calculations performed in the presented work
original Lichteneckers formula that was proved to be satisfactory for evaluation
of moisture dependent thermal and hygric properties of porous building materials
[9]. Also the application of four phase models looks promising. However, in case
of the masonry studied in this work, determination of amount of bound water
represents very complex problem.
The Lichteneckers equation adjusted for the studied masonry wall assumes
that the effective hygric and thermal parameter of the considered material
satisfies equation

peff f b pb f m pm ,
k

(1)

where peff is calculated effective parameter of masonry, fb volumetric fraction of


walling blocks in masonry, fm volumetric fraction of mortar, pb measured
material parameter of walling block, pm measured parameter of mortar, and k is
free parameter describing basically the path from the anisotropy at k = -1.0 to
another anisotropy at k = 1.0. However, the Lichteneckers equation may be also
applied for isotropic materials. On the basis of previous experience, we have
used the value of the parameter k = 0.
The effective parameters of multi-phase material cannot exceed the bounds
given by the parameters of particular fractions of its constituents. Here, the
Wiener bounds according to the Wieners original work were used [9]. These
bounds can be expressed by the following relations

peff

1
n

i 1

fi
pi

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(2)

148 Materials Characterisation V


n

peff f i pi ,

(3)

i 1

where Eq. (2) represents the lower limit and (3) the upper limit of the
investigated effective material parameter (fi is the volumetric fraction of the
particular phase, in our case argillite, sandstone and mortar), pi its material
parameter).

5 Studied masonry
For application of homogenization theory for the evaluation of the effective
hygric and thermal parameters of masonry, the typical fragment of the wall was
constructed in a simplified way similar to common brick masonry as shown in
Figure 1.

Figure 1:

Scheme of the reference masonry wall (dimensions in mm).

Using this scheme, the volumetric fractions of the particular materials in the
wall were calculated. The volumetric fraction of walling materials is equal to
0.824, whereas the volumetric participation of mortar is 0.176. Within the
calculations, effective parameters of two different walls were accessed. The
studied walls consisted always of lime based metakaolin mortar, and of one
walling material, nominally sandstone or argillite.

6 Results and discussion


Basic properties of all tested materials are summarized in Table 1. Each result
represents the average of five measured values. All the studied materials have
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Materials Characterisation V

149

proved high porosity, what is very positive factor from the point of view of their
presumed application in reconstruction of historical buildings.
Water vapour transmission properties of masonry materials are presented in
Table 2. We can see systematically very low values of water vapour resistance
factor what is again very prospective finding for application of all tested
materials in historical masonry. Since the historical masonry usually exhibits
increased moisture content, there is necessary to apply within the reconstruction
processes such materials that will allow moisture evaporation from the renovated
structures within the warm periods of the year.
Table 1:
material
sandstone
argillite
lime-metakaolin
mortar
Table 2:

Basic material properties of masonry materials.


bulk density
(kg/m3)
1807
1353
1690

matrix density
(kg/m3)
2627
2235
2620

total open
porosity (-)
0.31
0.39
0.35

Water vapour transmission properties of masonry materials.

material

sandstone
argillite
lime-metakaolin
mortar

dry cup arrangement, 0 50%


water vapour
water vapour
water vapour
permeability (s)
diffusion
resistance factor
coefficient (m2/s)
(-)
2.4E-11
3.3E-06
7.0
2.9E-11
4.1E-06
5.7
1.8E-11
2.5E-6
10.1

In Table 3, there are presented the effective diffusion parameters of studied


stone masonry calculated on homogenization principles. For verification of
calculated results, also the limiting bounds of effective parameters are presented.
Looking at the obtained data of water vapour transmission properties, one can
see that all the effective parameters lie between the Wieners bounds which
basically verifies their correctness.
Effective moisture diffusivity as function of moisture content is given in
Figures 2, 3. We can see high dependence of this moisture transport parameter
on moisture content. This materials behaviour significantly affects the
hygrothermal performance and consequently the durability. Systematically, the
highest moisture diffusivity exhibits sandstone. Its highly porous structure
formed by high radius pores allows fast liquid moisture transport in comparison
with argillite that is characteristic also by high total open porosity, but its pore
size is much smaller and structure more fine-grained.

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150 Materials Characterisation V


Table 3:

Water vapour transmission properties of stone masonry.

Sandstone wall homogenization, dry cup arrangement 0-50% RH


water vapour
permeability (s)

water vapour
water vapour
diffusion
resistance
coefficient (m2/s)
factor (-)

Wieners lower bound

2.29E-11

3.11E-06

7.40

Wieners upper bound

2.24E-11

3.05E-06

7.55

Lichtenecker model, k=0

2.27E-11
3.08E-06
7.47
Argillite wall homogenization, wet cup arrangement 0-50% RH
water vapour
permeability (s)

water vapour
water vapour
diffusion
resistance
coefficient (m2/s)
factor (-)

Wieners lower bound

2.74E-11

3.73E-06

6.17

Wieners upper bound

2.61E-11

3.55E-06

6.47

Lichtenecker model, k=0

2.69E-11

3.65E-06

6.30

Figure 2:

Effective moisture diffusivity of sandstone masonry.

The calculated effective sorption isotherms of studied masonry are given in


Figures 4 and 5. Typically, the highest capacity for water vapour adsorption can
be observed for lime-metakaolin mortar. However, in hygroscopic moisture
range, the highest values of adsorbed moisture were measured for argillite. The
data obtained for sandstone were systematically the lowest.
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Materials Characterisation V

Figure 3:

Effective moisture diffusivity of argillite masonry.

Figure 4:

Effective sorption isotherm of sandstone masonry.

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152 Materials Characterisation V

Figure 5:

Effective sorption isotherm of argillite masonry.

Measured and calculated thermal conductivity of all studied materials and two
types of masonry is presented in Figures 6 and 7. The values of effective thermal
conductivity in dependence on moisture content are systematically between the
range of Wieners bounds, which basically proves reliability of applied
homogenization technique.

Figure 6:

Effective thermal conductivity of sandstone wall.

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Materials Characterisation V

Figure 7:

153

Effective thermal conductivity of argillite wall.

7 Conclusions
An example of application of homogenization technique for determination of
hygric and thermal parameters of the stone masonry was introduced in the paper.
The obtained results indicate that the Lichteneckers equation may be
successfully used for such type of applications. Nevertheless, there is still an
open task to verify the reliability of applied homogenization model by laboratory
experiments that should confirm or controvert the presented results.

Acknowledgement
This research has been supported by the Czech Ministry of Education, Youth and
Sports, under project No MSM 6840770031.

References
[1] Pavlkov, M., Pavlk, Z. & ern, R., Hygric and Thermal Properties of
Materials Used in Historical Masonry. Proc. of the 8th Symposium on
Building Physics in the Nordic Countries, Technical University of Denmark:
Lyngby, pp. 903-910, 2008.
[2] Vejmelkov, E., Pavlk, Z., Fiala, L., Pavlkov, M. & ern, R., Heat and
Moisture Transport Properties of Stone Masonry Materials. Proc. of the
Building Physics Symposium, Katolieke Universiteit Leuven, Leuven, pp.
113-116, 2008.

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154 Materials Characterisation V


[3] Pavlk, Z., Michlek, P., Pavlkov, M., Kopeck, I., Maxov, I. & ern,
R., Water and Salt Transport and Storage Properties of Men Sandstone.
Construction and Building Materials, 22(22), pp. 1736-1748, 2008.
[4] Pavlk, Z., Identification of parameters describing the coupled moisture and
salt transport in porous building materials, CTU Prague, p. 145, 2009.
[5] EN ISO 12572, Hygrothermal performance of building materials and
products, determination of water vapour transmission properties, the
European Committee for Standardization, Brussels, 2001.
[6] JIikov M., Application of TDR Microprobes, Minitensiometry and
Minihygrometry to the Determination of Moisture Transport and Moisture
Storage Parameters of Building Materials, CTU Prague, p. 102, 2004.
[7] Roels S., Carmeliet, J., Hens, H., Adan, O., Brocken, H., ern R., Pavlk
Z., Hall Ch., Kumaran K., Pel L. & Plagge R., Interlaboratory Comparison
of Hygric Properties of Porous Building Materials. Journal of Thermal
Envelope & Building Science, 27(4), pp. 307-325, 2004.
[8] Roels, S., Carmeliet, J., Hens, H., Adan, O., Brocken, H., ern, R., Pavlk,
Z., Hall, C., Kumaran, K., Pel, L., A Comparison of Different Techniques to
Quantify Moisture Content Profiles in Porous Building Materials. Journal of
Thermal Envelope & Building Science, 27(4), pp. 261-276, 2004.
[9] Pavlk, Z., Vejmelkov, E., Fiala, L., ern, R., Effect of Moisture on
Thermal Conductivity of Lime-Based Composites. International Journal of
Thermophysics, 30(6), pp. 1999-2014, 2009.

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155

3D FIB reconstruction and characterisation of


a SOFC electrode
S. Chupin, N. Vivet, D. Rochais & E. Bruneton
CEA-Le Ripault, France

Abstract
SOFC (Solid Oxide Fuel Cells) appear to be a great alternative way to produce
electricity from hydrogen with high efficiency and no greenhouse gas emissions.
SOFC are efficient at high temperatures (around 800C) and are meant to be
used for stationary applications as heat and electric co-generation devices. To
understand how gases, electricity and heat flow through these media and to
improve their efficiency, it is critical to know the actual microstructure of these
electrodes. The studied electrodes are Ni-YSZ cermets in which characteristic
element sizes are around 1m. The 3D microstructure has been reconstructed
using FIB (Focused Ion Beam) tomography. This technique has been used on
several samples (different Ni-YSZ proportions) and gives representative 3D
volumes of around 101010m with a 10nm resolution. Theses 3D volumes are
then analysed to extract some important structural parameters such as volumetric
proportions, active surfaces, connectivity of each components and three phase
boundaries (TPB). Then, the 3D reconstructed volumes have been used to
determine homogeneous media equivalent properties such as thermal, ionic and
electric conductivities. These homogeneous equivalent properties are estimated
using a hot guarded plate simulation that takes into account each component
properties and the 3D structure.
Keywords: SOFC, FIB, tomography, thermal conductivity.

1 Introduction
Solid oxide fuel cell (SOFC) based-technology is one of the most promising
energy conversion systems due to its high efficiency and fuel flexibility [1]. The
materials involved in their constitution have become increasingly sophisticated,
both in composition and microstructure. One of the most common anode
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156 Materials Characterisation V


materials for SOFC is a porous Ni-YSZ cermet. The most important
requirements for the anode are catalytic activity, stability, ionic conductivity,
compatibility and porosity. For most of these conditions some experimental
studies can be investigated to estimate the corresponding parameters. Recently,
3D reconstructions of SOFC electrodes have been performed by X-ray computed
tomography (XCT) [2, 3] and mainly by focused ion beam - scanning electron
microscopy (FIB-SEM) [47]. FIB tomography principle consists in ablating a
structure physically by FIB slicing (Ga+ ions) followed by a digital
reconstruction since SEM images are collected after each ablation step. The
obtained images are then aligned and superimposed in order to generate the
volume [8].
In the present study, the optimization approach to obtain a high quality 3D
reconstruction of a Ni-YSZ anode using FIB-SEM is described first. Then, from
these 3D data, various microstructural parameters, and interfacial parameters are
quantified. Moreover, by solving the diffusive transport equation on the analysed
volume the effective thermal, electrical and ionic conductivities of the sample
have been estimated.

Experimental

2.1 Preparation of the anodic cermet


The deposition of the analysed NiO-8YSZ anode has been performed by screenprinting onto circular 8mol.% yttria doped-zirconia (8YSZ) supports using ink
with optimized composition and viscosity. The anode is a three layers coating on
the electrolyte substrate. NiO from J.T. Baker (USA) and 8YSZ from Tosoh
(Japan) have been used as raw materials to prepare the NiO-8YSZ cermet at
different Ni volume ratio. The preparation has been done to expect the 8YSZ/Ni
volume ratio to be 60/40.

Figure 1:

Schematic representation of the experimental method used to obtain


the 3D reconstruction of the SOFC anode from FIB tomography.

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157

2.2 FIB procedure


The image set has been collected with a FEI dual-beam Strata 400-S FIB system.
The procedure to obtain the 3D data from the initial sample is schematically
presented in Figure 1.
2.2.1 Preparation of the sample and of the region Of interest (ROI)
In order to easily distinguish the pores during SEM observation and to avoid
mistakes due to the depth of field in the SEM images, the sample has been
infiltrated with an epoxy resin under vacuum. To protect the sample from
accidental ion milling and erosion, a representative cross sectional area of the
sample has been located by electron imaging and coated with a Pt protective
layer of 2-3m (Figure 2) using an in-situ metallorganic ion source. Above all, Pt
deposition associated with sample infiltration and surface polishing were
necessary to avoid, or at least strongly reduce, a common artefact so-called
waterfalling or curtaining effect. The FIB has been used to mill wide and
deep trenches around the ROI with a maximal aperture current of 21nA,
constituting a U-shaped trench [9]. A quite high dimension free space around
the ROI is essential to prevent re-deposition of the sputtered material during the
sectional milling process. If the space around the ROI is too small, images with
high concentration of artefact features or uneven brightness are obtained.

Figure 2:

SEM image of the sample before the milling and imaging


procedure. The stage tilt is kept constant at 52 from the electron
beam while the sample surface (xz plane) is perpendicular to the
ion beam (y direction). The region of interest (ROI) is displayed in
the orange rectangle. The sample is sliced in the z direction. The
small rectangle on the Pt deposition (reference mark) is used to
measure the interslice (z) and correct from drifting effects.

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158 Materials Characterisation V


2.2.2 Milling and imaging process
Since the milling and imaging procedure is very time consuming, uncorrected
drift of electron beam, stage and sample can greatly affect the interslice real
value. For this reason a correction procedure has been used [10]. The SEM and
FIB operating conditions for the sequential ion milling and electron imaging
have been optimized. The FIB milling has been performed with an ion-beam
current of 460 pA at 30 kV. For SEM imaging, a magnification of 12 kX and a
Through the Lens Detector (TLD) operating in BSE mode with low scan rate
have been used. As the difference between the backscatter coefficients of Ni and
8YSZ are maximum for accelerating voltage smaller than 1kV, a 0.5kV
accelerating voltage has given an optimal contrast between Ni (bright), 8YSZ
(grey) and pores (dark) (Figure 3(a)). In this case, 115 images have been
recorded using a manual procedure along the sample thickness (Figure 3(a)).
2.2.3 Data processing
Data processing includes the following steps: i) alignment of the consecutives
slices, ii) correction of the dimensions taking into account the tilt of the electron
beam, iii) thresholding of the grey levels and labelling of phases, iv) resampling
of the data to obtain cubic voxels and v) 3D image generation. Most of the
processing steps have been performed using the AVIZO 6.2 software [11].

Figure 3:

Images of:(a) one of the original 115 serial-sections collected with


a BSE detector, so that Ni appears brighter than 8YSZ and that the
impregnated pores appear dark, (b) final 3D image after alignment,
delineate, cropping and adjustment of voxel size operations
showing Ni (bright), 8YSZ (grey) and pore (dark) phases.

The absolute dimensions in the x direction are obtained from a calibrated


SEM magnification. Because of oblique SEM imaging at an angle of 52,
distances in the y direction have been corrected. The 3D image dimensions is
finally 8.669.7911.41m3 (volume= 967.36m3 corresponding to about 1
billion voxels).

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159

3 Quantification results and discussion


First, volume fractions of each phase and their corresponding connectivity across
the analysed volume have been determined. The interfacial planes surface area
between two phases and the three phase boundaries lines length have been
evaluated. Then, effective thermal, electronic and ionic conductivities have been
estimated by solving numerically the diffusive transport equation. The most part
of this quantitative analysis has been performed with home made C programs on
a personal computer [dual CPU Intel Xeon E5440 @ 2.83GHz, 32 GB RAM].
3.1 Volume fraction
The volume fractions calculated from 3D data have given the following results:
41% for pores, 33% for 8YSZ and 26% for Ni. The solid volume fractions have
been estimated to 44% Ni and 56% 8YSZ in the studied anode, which are in
good agreement with the expected values (40 vol.% Ni / 60 vol.% 8YSZ). This
result provides evidence of the good representativity of the analysed volume.
3.2 Volumetric connectivity
In order to check the connectivity of each phase, a home made program based on a
Hoshen-Kopelman algorithm has been used [12]. The voxels linked together by a
face form a cluster [13]. When two voxels are only linked by a vertex or an edge,
they are not considered to be connected. Finally, if a cluster is connected to the six
boundary faces of the studied volume it is defined as percolated (Figure 4).

Figure 4:

Ni clusters representation showing that the main part (87.4%) of the


Ni phase is percolated, i.e. in contact with the six boundary faces of
the volume (in yellow).

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160 Materials Characterisation V


This analysis reveals that the three phases are mainly constituted of a very
large percolated cluster which represents 99.8%, 99.1% and 87.4% of pore,
8YSZ and Ni total volume respectively. This high percolation of all the three
phases suggests good transport ability for gases in the pores, as well as for
charge carrier in the solid phases.
3.3 Interface properties
Electrochemical and catalytic activities of an electrode are generally described
by only one parameter: the TPBL which is correlated to the number of regions
where the electrochemical reactions is able to take place. However not all of
them may be active due to non-contiguous regions (isolated cluster). So, the
specific surface and interface areas have been calculated only inside the
percolated volumes.
In the pie diagram of Figure 5, the specific interface areas are indicated. Thus,
about 50% of the total nickel surface is exposed to the porous phase and can be
used for surface catalytic reactions with the fuel.

Figure 5:

Pie diagram representing the specific surface areas of pores, 8YSZ


and Ni and the specific interface areas between the three
neighbouring phases (surface and interface are normalized by
volume sample). The active TPBL is 7.4m.m-3.

The TPB are the regions where the three phases (pores, 8YSZ, Ni) meet each
other. The TPB analysis procedure has been apply first to the initial volume and
yields to a TPB density of 11.2m.m-3. The activity of a TPB is subject to
numerous definitions in the literature. The major part of the authors defined a
TPB as active, if it lies three percolated phases (pore, Ni, 8YSZ) [4, 7]. The
active TPBL has been calculated and equal to 7.4m.m-3. This value is
relatively high compared to those reported in the literature. This suggests a high
electrochemical performance for the studied electrode.
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161

3.4 Effective conductivities calculations


3.4.1 Effective diffusion coefficient calculation
In the absence of external sources and in the case of the steady state condition,
the distribution of (for all conduction or diffusion phenomena) in the material
is governed by the diffusive transport equation [14]:

. D 0

(1)
D is defined as the diffusion coefficient in the material. Each voxel is
considered uniform with a given diffusion coefficient depending of its phase
(Dvoxel. Table 1). This equation is solved using an implicit finite difference
method based on a conjugate gradient algorithm [14]. Different Dirichlet
boundary conditions are fixed on two opposite faces ( 1 on one face and

on the opposite). Null Neumann boundary conditions are imposed on

the other faces. Once the distribution within the volume is obtained
(Figure 6), the average flux () over a cross section of surface area S can be
calculated:


D voxel . n dS

(2)

S
Table 1:

Thermal, ionic and electronic conductivities at 1123 K of pores,


8YSZ and Ni data [1721].
(W.m .K )
ionic (10-3 S.cm-1)
electronic (S.cm-1)
-1

Figure 6:

-1

Pores
(H2) 0.48
0
0

8YSZ
2
14
10-6

Ni
50
10-5
104

Reconstructed 8YSZ-Ni SOFC Anode and the electric field


resulting of a 1V potential difference between two opposite faces.

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162 Materials Characterisation V


For the equivalent homogeneous material, the average conduction flux can
be written [14]:

Deff S

1 2

(3)

xi max

The combination of eqns (2) and (3) leads to estimate Deff as:

Deff

Dvoxel
xi
S 1 2 S
xi max

dS

(4)

At 1123K and under one atmosphere the mean free path of H2 is around
900nm, and is bigger than our voxel size [15]. Then the concentration cannot be
considered uniform in a voxel and the bulk diffusion assumption is not valid
anymore. In the case of electron, ion and heat transport the corresponding mean
free path are smaller than 100nm. So, only heat, ion and electron diffusive
transport have been calculated in this work.
The results are given in Table 2 where the different values of Deff are reported
under the form of thermal, electronic and ionic effective conductivities. The
effective thermal conductivity appears quite isotropic with a slighter lower value
in the z direction, close to 4 W.m-1.K-1. This value has the same order than those
generally reported for SOFC anodes [16].
Table 2:

Thermal, electronic, ionic effective conductivities in the x, y and z


directions from the calculation of Deff at T= 1123 K.
(W.m .K )
ionic (10-3 S.cm-1)
electronic (S.cm-1)
-1

-1

x
4.23
1.43
281

y
4.54
1.19
252

z
3.27
1.03
66

The effective electronic conductivity appears anisotropic: the electronic value in


the z direction is smaller than the ones in the x and y direction. The evolution of
the Ni concentration along each axes has shown that the Ni proportion along z in
more important than along the other axes. It creates a stricture effect that
decreases the effective conductivity. Experimental four-point electrical
measurements performed at 1123 K on the anode surface lead to a value of the
same range: 81 S.cm-1.
Ionic conductivity in the studied anode is quite isotropic and close to 10-3. As
a value of 1.4 10-2 had been used for the calculation, the microstructural effect
for the loss of conductivity is closed to a factor 10.

4 Conclusion
This work has focused on the 3D analysis of the microstructure in a Ni-8YSZ
SOFC anode reconstructed by FIB tomography. Sample preparation, milling and
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imaging conditions and data processing have been optimized to obtain a high
quality representative 3D microstructure having the following dimension of
8.669.79 11.41m3. Home made programs have led to the calculation of some
microstructural parameters such as volume fraction, connectivity, specific
surface and interface areas and TPB length including the proportion of active and
non active ones. These calculations have shown that for an anode with an initial
8YSZ/NiO volume ration of 60/40 leading after reduction to volume relative
amounts 41% of pores, 33% of 8YSZ and 26% of Ni, all the phases were highly
percolated. The active TPB length has been estimated as 7.4m/m3 which
comparing to the literature results corresponds to an effective anode. By solving
the diffusive transport equation with finite difference calculations, the effective
thermal, electronic and ionic conductivities could be determined.

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Modelling of load transfer between


porous matrix and short fibres in
ceramic matrix composites
J. G. P. Silva1,2, D. Hotza1, R. Janssen2 & H. A. Al-Qureshi1
1
2

Federal University of Santa Catarina (UFSC), Florianpolis, SC, Brazil


Technical University of Hamburg-Harburg(TUHH), Germany

Abstract
The aim of this work is to present a model of load transfer between porous
matrix and short fibres in ceramic matrix composites. This analysis is based on
the earlier shear-lag models used for polymeric composites. However, geometry
and strength of fibres in addition to the matrix porosity are included in the
present analysis. The theoretical curves for the longitudinal and shear stresses
distributions along the fibre-porous matrix interface are presented. They
exhibited a maximum strength point at the middle of the short fibres. It became
evident that the critical length is governed by the relative properties of the fibres,
matrix and porosity, which greatly influenced the load carrying capacity of the
fibres in the composites. In addition, the present simplified solution facilitates
the understanding of the interface mechanism using porous matrix.
Keywords: modelling, ceramic matrix composites, shear-lag models, porous
ceramics.

1 Introduction
Modern structural ceramic composites possess a number of unique properties
that cannot be achieved by other materials. Therefore, they have a potential for
saving energy, reducing wear, and increasing the lifetime of components [1].
However, regardless of their remarkable properties, structural ceramics are not as
widely used in industry as they should and could be. Among the reasons for the
reluctance of industry to introduce structural ceramic as components are [1]:
high price of ceramic parts,
insufficient knowledge in traditional metal-oriented engineering,
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166 Materials Characterisation V


low toughness,
need of redesigning components to meet specific requirements.
In the case of ceramic composites, the price factor is still the major limitation
in terms of commercial applications. This is especially true for components made
of composites with complex structures and requiring mechanical performance
and reliability. To this aim, fibre-reinforced ceramic composites have been
developed to overcome the fragility and unreliability of monolithic ceramics.
Their main advantages are high-temperature resistance, low density, better
corrosion resistance and adequate damage tolerance [2].
There is a wide range of fibre-reinforced ceramic composites depending on
the chemical composition of the matrix and reinforcement, although currently
only Cf-C/SiC composites produced by silicon infiltration have reached
commercial production. However, fibre-reinforced ceramic composites based on
oxides (alumina, mullite) can provide key benefits about long-term stability
under oxidizing atmospheres [2].
Despite considerable interest in oxide ceramic composites in the past decade
[35], there is still no production concept that meets the requirements in view of
cost and performance.
This study aims to investigate the load transfer phenomenon in ceramic-ceramic
short fibre composites, using a simplified mathematical model that aims to predict
the actual effectiveness of reinforcement depending on the material properties.

2 Modelling
2.1 Previous considerations and analysis
Considering a loaded composite made of a dense fibre with length 2L embedded in
a porous matrix made of the same material of the fibre, hereby is assumed that no
slippage occurs between fibre and matrix. It should be also considered that the
Poissons ratio of fibre and matrix is the same, which implies on the inexistence of
transversal stress when the loading is applied along the fibre. Considering the
displacements in the fibre u and far away from the fibre v: (Fig. 1):

Figure 1:

Simplified scheme of the stress field around the fibre. (a) without
loading; (b) loaded [6].

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Materials Characterisation V

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From Hookes law:

E
A
L

(1)

Taking the differential:

dP EA d

dx
L dx

(2)

Cox proposes a similar behaviour [7]:

dPf
dx

B (u v )

(3)

where Pf is the load acting on the fibre and B is a constant that depends on the
fibre distribution and the Youngs Modulus of fibre and matrix.
Differentiation of Eq. (3) leads to:

d 2 Pf
dx

du dv
B
dx dx

(4)

The derivatives of u and v can be taken as the deformations in the fibre and
matrix, respectively:

Pf
du

dx Af E f

(5)

dv

dx

(6)

Substitution of (5) and (6) in (4), gives:

d 2 Pf
dx

B f
Af E f

(7)

A solution to this differential equation leads to:

Pf E f A f S sinh x T cosh x
where:

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168 Materials Characterisation V

B
E f Af

(9)

and S and T are constants defined by the boundary conditions.


To simplify the solution, instead of the stress distribution proposed by Cox, a
model proposing that the stress drop in the extremity of the fibre follows a
quadratic behaviour.
To evaluate the model herein described, it is possible to apply the equations to
a model composite, made of a porous alumina matrix and alumina fibres. Table 1
summarizes the properties that are relevant for the calculation.
Table 1:

Properties of the model composite.

Property
Fibre volume fraction
Matrix porosity fraction
Fibre length 2l (mm)
Fibre diameter (m)
Ratio Critical length/Length or

Value
0.45
0.24
50.8
10
0.25

2.2 Proposed model


According to Fig. 2, let us consider a composite with fibres whose length is 2L,
diameter 2r and Youngs modulus Ef, embedded in a matrix with porosity ,
made of the same material of the fibre. Hereby we define the critical length Lc, in
which from the tip of the fibre the stress distribution isnt constant by the shearlag between matrix and fibre. It is more feasible to work with , the ratio
between the critical length and fibre length, being Lc =L.

Figure 2:

Proposed stress distribution and boundary conditions.

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Materials Characterisation V

169

It can be proposed that the stress distribution between the points L-L and L
follows a behaviour such as:

f ( x ) Ax B

(10)

By using the boundary conditions given in Fig. 2, and substituting them in (10):

E f A( L L) B

(11)

(1 ) E f AL B

(12)

Isolating B in (12) and replacing in (11):

(1 ) E f AL E f A( L L)

(13)

E f A L

(14)

And then:

Ef
L

(15)

By replacing A from (12):

(1 ) E f

Ef
B

(16)

Therefore, B is given by:

B 1 1 E f

(17)

By replacing the constants in (10), we have the stress distribution behaviour:

f ( x)

Ef
1

x 1 1 E f
L

(18)

To determine the shear stresses along the fibre, the force equilibrium in a
fibre element with diameter 2r and length dx is made in the x direction, resulting
in:
(19)
r 2 2 rdx 0
Then, the shear stresses are given by:

r d
2 dx

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170 Materials Characterisation V


By the differential of (18):

f ( x)

Figure 3:

r E f
2 L

(21)

Stress distribution along the fibre for different matrix porosities.


=0.25.

Figure 4:

Force equilibrium in a fibre element whose length is dx.

With the stress distribution along the fibre, it is possible to calculate the
average stress carried by the fibre in the composite, given by:

1 L
f ( x )dx
L 0

(22)

For 1, i.e. the fibre is shorter than the critical length:

1 L Ef
1

x 1 1 E f dx

0
L
L

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Materials Characterisation V

Figure 5:

171

Shear stress distribution along the fibre for different matrix


porosities. =0.25.

Then,

Ef
f 1
2

(24)

And for 0 < < 1, i.e., the fibre is longer than the critical length:

L L

E f dx

L L

f ( x )dx

(25)

Therefore:

f E f 1

(26)

With the average stresses well defined, we can define the stresses in the ply
longitudinal and transversal directions. When the matrix material is the same as
the fibre, it is possible to write the elastic modulus of the matrix as a function of
the fibre modulus:

Em E f e bp
where b is a shape factor that depends on the pore shape and distribution.

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172 Materials Characterisation V

Figure 6:

Longitudinal resistance of the composite [6].

The stress on the transversal direction is proportional to the matrix maximum


stress, given by:

T m E f e bp

(28)

The stress on the longitudinal direction is given by the average value between
matrix and fibre, based on the volumetric fractions of fibre and matrix:

L m 1 f f f 1 f E f e bp f f

(29)

Therefore for 0 < < 1:

L 1 f E f e bp E f 1


f
2

(30)

And for > 1:

L 1 f E f e bp E f 1

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f
2

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Materials Characterisation V

Longitudinal ply ultimate strength, for different .

Figure 7:

Figure 8:

173

Longitudinal ply ultimate strength for different porosities.

3 Conclusions
A load transfer model was proposed to ceramic composites, which relates the
matrix porosity and fibre length with the mechanical strength of such
composites. It is hoped that the experimental validation of the model can be
established or any changes aimed at increasing its accuracy can be made.

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174 Materials Characterisation V

Acknowledgements
The authors would like to thank the agencies CAPES (Coordenao de
Aperfeioamento de Pessoal de Nvel Superior), CNPq (Conselho Nacional de
Desenvolvimento Cientfico e Tecnolgico) and DFG (Deutsche
Forschungsgemeinschaft), for funding this research under grant Bragecrim
015/09.

References
[1] Janssen, R., Scheppokat, S. & Claussen, N., Tailor-made ceramic-based
components Advantages by reactive processing and advanced shaping
techniques. Journal of the European Ceramic Society, 28, pp. 1369-1379,
2008.
[2] Janssen, R. & Hotza, D. Low-cost and reliable production of oxide ceramic
matrix composites, Bragecrim Project Proposal, December 2008.
[3] Wendorff, J., Janssen, R. & Claussen, N., Saphirfaserverstrkung
reaktionsgebundener
oxider
Keramiken.
Verbundwerkstoffe
und
Werkstoffverbunde, ed. G. Ziegler, pp. 421-424, 1996.
[4] Lundberg, R. & Eckerbom, L., Design and processing of Al-oxide
composites. Ceramic Transactions, 58, pp. 95-104, 1995.
[5] Levi, C.G., Yang, J.Y., Dalgleish, B.J., Zok, F.W. & Evans, A.G.,
Processing and performance of an all-oxide ceramic composite. Journal of
the American Ceramic Society, 81, pp. 2077-2086, 1998.
[6] Casaril, A.; Gomes, E.R.; Soares, M.R.; Fredel, M.C. & Al-Qureshi, H.A.,
Anlise micromecnica dos compsitos com fibras curtas e partculas.
Matria, 12(2), pp. 408-419, 2007.
[7] Cox, H.L., The elasticity and strength of paper and other fibrous materials.
British Journal of Applied Physics, 3, pp. 72-79, 1952

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Materials Characterisation V

175

Modeling aspects concerning the axial behavior


of RC columns
H. O. Koksal1, T. Turgay 2, C. Karako3 & S. Ayenk4
1

Construction Technology Program, anakkale Onsekiz Mart University,


Turkey
2
Faculty of Engineering and Architecture, Abant zzet Baysal University,
Bolu, Turkey
3
Civil Engineering Department, Boazii University, Turkey
4
M.S. Student, Civil Engineering Faculty, Yldz Technical University,
Turkey

Abstract
This paper is concerned with the axial behavior of the RC columns. Stress-strain
relationships of experimentally tested RC columns under concentric loading are
compared with the predictions of the Koksal model. Moment-curvature analyses
of RC sections are also performed employing the same model in a self-developed
moment-curvature program for confined concrete. Results are compared with the
output of EXTRACT which uses the Mander concrete model.
Keywords: confinement, reinforced concrete columns, concentric loading,
stressstrain relations.

1 Introduction
Confining pressure on RC columns increases the concrete strength. Transverse
reinforcements such as steel stirrups, FRP wraps, and steel jackets create a triaxial compressive stress state producing confinement action around the concrete
core. Extensive research on the improvement of concrete confinement has been
carried out since the pioneering study of Richart et al. [1]. The constitutive
model for confined concrete plays an important role on the accuracy of the
moment-curvature curves to perform a reliable pushover analysis of RC frames.
There are some frequently cited models (Hognestad [2], Kent and Park [3],
Sheikh and Uzumeri [4], Mander et al. [5], Saatcioglu and Razvi [6]) to predict
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176 Materials Characterisation V


the peak stress or the stressstrain curve of confined concrete. Kksal has also
proposed a failure criterion for concrete under tri-axial compression stress state
[7]. In this paper, four square RC columns tested in Yldz Technical University
(Turgay [8], Kksal et al. [9]) are evaluated implementing Koksal model. The
flexural behavior of the columns is also simulated and their moment-curvature
relations corresponding to different axial load levels are obtained using the same
model. Moment-curvature curves are compared with the outputs of EXTRACT.

2 Experimental study
The square specimens in the test program have 200x200 mm cross-section
dimensions and 1000 mm height. The columns were tested in the structural
laboratory of Yldz Technical University [8]. Figure 1 shows the details of test
setup and instrumentation for the two specimens.

Figure 1:

Test setup and details of test specimens C1L4S8 and C1L8S8 [8].

The experimental study was limited to one type of concrete mix design
typically. C1 type columns are tested at 30 days. All longitudinal bars are 10mm
in diameter and L4 and L8 shows the number of the bars in the cross-section of a
column. The tie spacing is 100mm and the S8 represents diameter of stirrups. For
measurement of axial strains, four linear variable displacement transducers
(LVDTs) are placed over the central 400mm gage length at each side of a
column in a similar way used to assess any eccentricity of the applied load as
recommended in the study of Shrive et al. [10]. Although the LVDT readings
were provided very close to each other, next to the maximum axial load there can
be a significant variation between the minimum and maximum values of
shortening reaching very high values [9]. Figure 2 shows the axial load-axial
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Materials Characterisation V

177

shortening curve for C1L8S8 for which almost perfectly homogeneous strains
were obtained. However, for other columns the differences between LVDT
readings are somewhat greater indicating a localized damage zone at one specific
region of the specimen.

Figure 2:

Four separate LVDT readings of axial load-shortening curves for


C1L8S8 [9].

3 Simulation of flexural behavior and moment curvature


relations
The limit state design procedure of reinforced concrete elements has undergone
major revision by most of the international codes in harmony with the
performance-based design engineering approach. In this approach, momentcurvature behavior of flexural members is needed to define the deflection
demand and to simulate the behavior of the reinforced concrete members under
lateral loads such as earthquake actions. Moment-curvature plots readily
illustrate stiffness, strength, and cross-sectional ductility, and allow the
calculation of deflections after materials become nonlinear. In a flexural member
the shear reinforcement or any other confinement mechanism applies pressure to
the concrete in the compression zone and affects energy dissipation capacity
directly. Therefore, to predict the moment-curvature behavior of a flexural
member, the stressstrain behavior of confined concrete under axial compression
is vital. With the development of performance-based design methods, there is an
increasing need for simplified but reliable analytical models capable of
predicting the flexural behavior of reinforced concrete members. The flexural
behavior of reinforced confined concrete sections is introduced by Koksal model
[7]. The failure criterion proposed by Koksal is given as:

f 1.1317 0.7645 2 k1, 2 ,3 0


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178 Materials Characterisation V

where k k f l , f c' , and are deviatoric and hydrostatic lengths, respectively.


In this equation k, as a function of the lateral confinement pressure, f l , and the
cylinder compressive strength of concrete, f c' can be expressed as [7] :
2

fl
fl

k 4.07 ' 0.89 ' 0.807 fc'

fc
fc

(2)

The theoretical confining pressure, f l , can be found in usual way as [11] :


or
(3)
f l , x k e sx f yh
f l , y k e sy f yh
In this relation, sx and sy are the confinement proportion both x and y
direction respectively, ke is the confinement effectiveness coefficient, and fyh is
the yield strength of transverse reinforcing steel. The Saenzs equation [12] is
adopted for describing the monotonic stress-strain relationship for confined
concrete:

1E0


E
1 0 2 1 1
cc cc
Es

(4)

where 1 and 1 are axial compressive stress and strain of concrete,


respectively; E0 is the initial tangent modulus of elasticity in MPa and can be
calculated as E0 4750 f co' ; Es is the secant modulus at the point of maximum
compressive stress f cc' which can be determined using Equation 1. The strain cc
corresponding to the maximum compressive stress f cc' can be found employing
the recommended relations of Richart et al. [1] :

cc ' c 1 k 2

fl
f 'c

(5)

where c' is the peak strain at the strength of plain concrete cylinders. In this
equation, k2 is taken as 5k1.
Figure 4 aims to compare experimental axial stress-strain curves of the four
column specimens with those predicted from Eqs (1)-(4).
In this study, a simple program is written in FORTRAN to produce momentcurvature plots for confined column section under bending and axial
compression. The cross section is divided into 1mm thickness slices. For a given
depth of natural axis, the strain at the extreme slice in compression is found by
iterative procedure. For each slices, the stress and strain are calculated using
force equilibrium and compatibility requirements respectively. Stress acting on
the core concrete (cover concrete is neglected) calculated using Koksals model.
Koksals model has also been utilized through the 3D finite element analysis of
RC and FRP-confined concrete columns [11, 13] successively. Figure 3(a)
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Materials Characterisation V

179

demonstrates the typical axial stress-strain curves recommended by Saenz for a


concrete member [12]. Finite concrete forces for unconfined and confined core
of each slice are found by multiplying stress by corresponding areas. Stress at the
reinforcement bars is found by entering a simple bi-linear stress-strain curve in
Figure 3(b) with the strain value found from compatibility requirements at each
load level. Finite forces on steel can be found by multiplying stress by the area of
the reinforcement.

Figure 3:

(a) Saenz curve for uniaxial behavior of concrete; (b) stress-strain


relation for steel.

Figure 4:

Experimental and predicted stress-strain curves for the specimens.

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180 Materials Characterisation V


Figure 5 show the moment-curvature relations for C1L4S8 and C1L8S8 at
various load levels. Increasing the axial load from 200kN to 400kN always
results an increase in the moment carrying capacity. But when a load near to the
axial load capacity is considered, moment carrying capacity does not increase
any more. Also decrease in the curvature is very obvious when the axial load
increases as expected.

Figure 5:

Moment-curvature diagrams for the four columns at various axial


load levels.

30

Moment (KNm)

C1L4S8

20

10
Model L200
EXTRACT L200
0
0

Figure 6:

20

40
60
Curvature x 10e6 (rad/m)

80

100

Output of EXTRACT program and the proposed model for


moment-curvature diagrams for C1L4S8 at the axial load level of
200kN.

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Materials Characterisation V

181

Figures 68 show the output of EXTRACT program [14] for C1L4S8


subjected to the axial load levels of 200kN, 400kN and 600kN respectively.
EXTRACT program employs the Mander model for confined concrete. There are
not significant differences if one compares the curvature values for both
programs.
40
C1L4S8

Moment (KNm)

30

20

10
Model L400
EXTRACT L400
0
0

20
40
Curvature x 10e6 (rad/m)

60

Figure 7:

Output of EXTRACT program and the proposed model for


moment-curvature diagrams for C1L4S8 at the axial load level of
400kN.

Figure 8:

Output of EXTRACT program and the proposed model for


moment-curvature diagrams for C1L4S8 at the axial load level of
600kN.

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182 Materials Characterisation V

4 Conclusion
This paper has been primarily concerned with the modeling aspects for the axial
behavior of RC columns. Experimental axial stress-strain curves of the four
column specimens are predicted employing Koksal model. Furthermore, a
spreadsheet-based program is constructed to produce moment-curvature plots for
the performance-based design engineering approach. The following conclusions
can be drawn based on the results of the analyses:
1. As can be seen in Figure 5, Koksal model successively predicts the axial
behavior of the four RC column specimens tested under concentric loading.
2. It can be easily observed that Koksal model results into somewhat higher
values for the moment carrying capacities than the outputs of EXTRACT
program which employs Mander model in Figure 68, but the general trend
of the curves are the same. The developed program gives 27kNm and 38kNm
for moment carrying capacities at the axial load levels of 400kN and 600kN
while EXTRACT program results are between 22kNm and 27kNm.

Acknowledgement
The support of Boazii University Research Fund (ref: research project 5232)
for this paper is gratefully acknowledged.

References
[1] Richart, F.E., Bradtzaeg, A. and Brown, R. L. 1928. A study of the Failure
of Concrete under Combined Compressive Stresses. Bulletin Np. 185,
Engineering experimental station University of Illinois, Urbana, pp. 104.
[2] Hognestad, E., 1951. A Study of Combined Bending and Axial Load in
Reinforced Concrete Members. Bulletin Series No.399, University of
Illinois Eng. Exp. Station, Urbana.
[3] Kent, D.C. and Park, R. 1971. Flexural Members with Confined Concrete.
Journal of the Structural Division, Proc. of the American Society of Civil
Engineers, 97(ST7), pp.1969-1990.
[4] Sheikh, S.A. and Uzumeri, S.M. 1982. Analytical Model for Concrete
Confinement in Tied Columns. Journal of the Structural Division, Proc. of
the American Society of Civil Engineers, 108(ST12), pp. 2703-2722.
[5] Mander, J.B., Priestly, M.J.N. and Park, R. 1988. Theoretical Stress-Strain
Model for Confined Concrete. Journal of the Structural Engineering,
ASCE, 114(8), pp.1804-1826.
[6] Saatcioglu, M. and Razvi, S.R. 1992. Strength and Ductility of Confined
Concrete. Journal of the Structural Engineering, ASCE, 118(6),
pp.1590-1607.
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Materials Characterisation V

183

[7] Kksal, H.O. 2006. A Failure Criterion for RC Members Under Triaxial
Compression. Structural Engineering and Mechanics, Techno-Press, 24(2),
pp.137-154.
[8] Turgay, T. CFRP Uygulanms_ betonarme elemanlarn performans (The
performance of FRP strengthened structural members). PhD thesis,
Submitted to Yldz Technical University; 2007.
[9] Kksal, H.O., Karako, C., Polat Z., Turgay T. and Akgn .
2007.Evaluation of Experimental Procedures for Confined Concrete
Columns. Computational Methods and Experimental Measurements XIII,
WIT Transactions on Modeling and Simulation, 46, 233-242.
[10] Shrive, P.L., Azarnejad, A., Tadros, G., McWhinnie, C. and Shrive, N.G.
2003. Strength of Concrete Columns with Carbon Fibre Reinforcement
Wrap. Canadian Journal of Civil Engineering, 30, pp. 543-554.
[11] Doran, B. 2009.Numerical simulation of conventional RC columns under
concentric loading. Material and Design, 30(6), 2158-2166.
[12] Saenz, L.P. 1964. Discussion of Equation for Stress-Strain Curve of
Concrete by Desai and Krishnan. ACI, 61(9), 1229-1235.
[13] Kksal, H.O, Doran, B., and Turgay, T. 2009. A practical approach for
modeling FRP wrapped concrete columns. Constr. and Build. Mat., 23(3),
14291437.
[14] EXTRACT-v.3.0.8, Cross section analysis program of structural engineers,
TRC/Imbsen Software Systems.

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Section 5
Innovative experiments

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Materials Characterisation V

187

Surface characterization of eucalyptus and ash


wood veneers by XPS, TOF-SIMS, optic
profilometry and contact angle measurements
G. Vzquez, R. Ros, M. S. Freire, G. Antorrena
& J. Gonzlez-lvarez
Department of Chemical Engineering,
University of Santiago de Compostela, Spain

Abstract
Composition and properties of the wood surface are very important in board
manufacture as they determine wood-adhesive bonding and the quality of the
final product. In this work two spectroscopic techniques, X-ray photoelectron
spectrometry (XPS) and time of flight secondary ion mass spectrometry (TOF
SIMS), have been employed to study the surface composition of eucalyptus
(Eucalyptus globulus) and ash (Fraxinus excelsior) sliced cut veneers. Both
wood species are widely used for decorative veneers in the finishing of wood
panels (particle boards, medium density fiberboards, etc.). Further
characterization of the wood surface was carried out by optic profilometry and
wettability analysis, using the sessile drop method to measure contact angles.
Wood is a very heterogeneous material and its composition can vary
significantly depending on the sampling area; then, the influence of the radial
position of the veneer in the trunk was also analyzed. From the low resolution
XPS spectra the oxygen to carbon (O/C) ratio was calculated and, resolving the
C1s signal, the percentages of the different carbon peaks corresponding to
different functional groups (C1, C2, C3 and C4 carbons) were also calculated.
The lower O/C ratio and the higher C1/C2 ratio for eucalyptus than for ash was
attributed to the higher concentration of extractives on the eucalyptus wood
surface that was confirmed by the TOF-SIMS spectra, which additionally
revealed a patchy distribution of the extractives. The higher hydrophobicity of
the eucalyptus wood surfaces was also supported by the results on the wetting
properties of the veneers. Eucalyptus veneers exhibited a significantly higher
constant wetting rate angle (cwra) and, consequently, a lower wettability than
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188 Materials Characterisation V


ash veneers, which can also be related with the higher values of the rugosity
parameters for the latter. There were no significant influences of the radial
position of the veneer on the surface properties.
Keywords: wood veneers, wettability, contact angles, XPS, TOF-SIMS, optic
profilometry.

1 Introduction
Wood is a renewable resource composed mainly of three polymers, cellulose,
hemicelluloses and lignin, and various extractives such as fatty acids, sterols,
tannins, etc. Wood surface characteristics condition the interaction with
adhesives and binders in wood based products and, therefore, have influence in
the quality of the final product. Several methods have been proposed to
characterize material surfaces. Contact angle analysis is one the traditional
methods for the characterization of surfaces on a macroscopic scale, and
provides information on surface wetting properties [1].
Surface chemical composition of complex materials such as wood can be
determined using two complementary spectroscopic techniques, X-ray
photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass
spectrometry (TOF-SIMS), the former generating more quantitative data and the
latter more qualitative data [2]. X-ray photoelectron spectroscopy (XPS) provides
the elemental composition for the outermost 510 nm surface layers and functional
groups, chemical bonding types, oxidation state, etc. can be additionally deduced
from XPS data. Time-of-flight secondary ion mass spectrometry (TOF-SIMS)
provides data for depths of 12 nm, including detailed chemical information via
identification of intact molecular ions or characteristic molecular fragments that are
emitted from the surface [3]. Additionally, it provides ion images, mapping the
lateral distribution of secondary ions signals from lignin, carbohydrates, extractives
and metals within an analyzed wood surface area [2, 4].
The aim of this paper was to evaluate and compare the surface properties and
composition of eucalyptus (Eucalyptus globulus) and ash (Fraxinus excelsior)
sliced cut veneers used as decorative veneers in the finishing of wood panels. A
wettability analysis, using the sessile drop method to measure contact angles,
was applied in combination with two spectroscopic techniques, X-ray
photoelectron spectrometry (XPS) and time of flight secondary ion mass
spectrometry (TOF SIMS). Roughness of the wood surface was analysed by
optic profilometry. Wood is a very heterogeneous material and its composition
can vary significantly depending on the sampling area; then, the influence of the
radial position of the veneer in the trunk was also analyzed.

2 Methods
2.1 Contact angle determination
Samples of eucalyptus (Eucalyptus globulus) and ash (Fraxinus excelsior) sliced
cut veneers with a humidity of 8% (wet basis) were used to prepare 2 cm (length)
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Materials Characterisation V

189

x 2cm (width) x 0.6 mm (thickness) wood pieces. Contact angle measurements


were made perpendicular to the grain direction of the wood according to the
sessile drop method using a Dataphysics OCA 15 Plus equipment (Filderstadt,
Germany) with a video measuring system with a high-resolution CCD camera.
The data were analyzed with the Dataphysics software SCA 20.
To compare the wettability of both wood species and to analyze the influence
of the radial position of the veneer in the trunk, 20% (by weight) aqueous
solutions of chestnut shell extracts, potential components of wood adhesives [5],
were used. Ten L drops were added and the variation of contact angle with time
was registered till 240 s.
Contact angles were calculated according to the Young-Laplace method. The
constant wetting rate angle (cwra) was determined as per Nussbaum [6] plotting
the wetting rate (d/dt, being the contact angle) against time and selecting the
value (cwra) corresponding to a constant wetting rate. Initial (0, t=0), final (f,
t=240 s) and cwra contact angles were calculated as the average of thirty
measurements on each wood species and radial position.
2.2 X-ray photoelectron spectrometry (XPS)
Analysis of the samples was performed using a Thermo Scientific K-Alpha
ESCA instrument equipped with aluminium Ka1,2 monochromatized radiation at
1486.6 eV X-ray source. Due to the non conductor nature of samples it was
necessary to use an electron flood gun to minimize surface charging.
Neutralization of the surface charge was performed by using both a low energy
flood gun (electrons in the range 0 to 14 eV) and an electrically grounded stain
steel screen placed directly on the sample surface.
The XPS measurements were carried out using monochromatic Al-K
radiation (h=1486.6 eV). Photoelectrons were collected from a takeoff angle of
90 relative to the sample surface. Measurements were done in a Constant
Analyser Energy mode (CAE) with a 100 eV pass energy for survey spectra and
20eV pass energy for high resolution spectra.
Charge referencing was done by setting the lower binding energy C1s
photopeak at 285.0 eV C1s hydrocarbon peak. The spectra fitting was based on
Chi-squared algorithm used to determine the goodness of a peak fit. Surface
elemental composition was determined using the standard Scofield
photoemission cross sections. The chemical functional groups identity was
obtained from the high-resolution peak analysis of carbon-1s (C1s) and oxygen1s (O1s) envelopes.
2.3 Time of flight secondary ion mass spectrometry (TOF SIMS)
The TOF-SIMS analyses were made on a TOF-SIMS IV (ION-TOF GmbH,
Germany).The sample was bombarded with a pulsed Bismuth ion beam. The
secondary ions generated were extracted with a 10 kV voltage and their time of
flight from the sample to the detector was measured in a reflectron mass
spectrometer. Mass spectra of positive and negative secondary ions were
acquired from randomly selected areas of 500 x 500 m2 on each sample. In all
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190 Materials Characterisation V


cases, a 25 keV pulsed Bi3+ beam at 45 incidence was used. Lowenergy
electron flooding was used for charge compensation. All analyses were done
under static SIMS conditions (1012 ions/cm3).
2.4 Optic profilometry
Interferometric profilometry measurements were carried out in the Vertical
Scanning Interferometry (VSI) mode using an Interferometric Microscope
WYKO NT-1100. For each sample, three measurements were carried out at a 5X
magnification (1.2x0.9 mm2), to determine statistically representative values of
surface roughness parameters, and a measurement at magnifications of 20X
(298x227 m2) and 50X (119x91 m2) to see the details of the surface
topography. Great field measurements covering an area of 3x2 mm2 at a 5X
magnification were also performed to obtain a more representative image of the
surface.

3 Results and discussion


3.1 Wettability of eucalyptus and ash wood veneers
Figure 1 shows the evolution of contact angle with time for an aqueous solution
of chestnut shell extracts on eucalyptus and ash veneers. For each species,
veneers obtained from different positions in the trunk, interior and exterior, were
compared. Throughout the time range tested, contact angles for eucalyptus
veneers were significantly higher than those for ash veneers. Additionally, for
both wood species there were not significant differences between the contact
angles for the interior and exterior veneers.

Figure 1:

Contact angle versus time for an aqueous solution of chestnut shell


extracts on interior and exterior eucalyptus and ash sliced veneers.

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The values calculated for the initial (t=0; 0), final (t =240 s; f) and constant
wetting rate (cwra) angles are presented in Table 1. Not only initial contact
angles but also final and constant wetting rate angles were remarkably higher for
the eucalyptus veneers. Higher contact angles are indicative of a worse wetting
behaviour and could be related with a greater migration of hydrophobic
substances to the surface of eucalyptus veneers [7]. Differences between the 0,
f and cwra values of interior and exterior veneers were almost negligible which
confirms the previous qualitative observation.
Table 1:

Initial (0), final (f) and constant wetting rate (cwra) angles for
exterior and interior veneers of eucalyptus and ash wood with an
aqueous solution of chestnut shell extracts.

Veneer
Eucalyptus
Ash

0 ()
99.72
(5.83)
75.22
(1.44)

Exterior
f ()
cwra ()
45.25
50.8
(1.88)
(0.11)
28.01
27.99
(0.37)
(0.37)

0 ()
95.34
(4.77)
73.42
(9.91)

Interior
f ()
cwra ()
46.70
50.12
(6.77)
(0.10)
27.75
30.6
(8.43)
(0.76)

(Standard deviation)

3.2 X-ray photoelectron spectrometry (XPS)


Figure 2a shows the XPS survey spectra of eucalyptus and ash samples of
interior veneers. The surface elemental compositions (in atomic %) for the
different sample groups are summarized in Table 2. The percentages shown are
the mean value of three determinations.
Table 2:

Surface elemental composition (in atomic %) for eucalyptus and


ash veneers.

Veneer
Exterior
eucalyptus
Interior
eucalyptus
Exterior ash
Interior ash

C
80.7
(2.2)
79.2
(0.1)
77.2
(1.0)
76.9
(1.4)

O
18.0
(2.3)
19.3
(0.7)
20.8
(1.1)
20.5
(1.2)

N
0.7
(0.2)
1.0
(0.4)
0.6
(0.1)
0.9
(0.1)

Si
0.6
(0.1)
0.8
(0.2)
1.2
(0.5)
1.2
(0.5)

Ca
0.3
(0.1)
0.5
(0.1)

(Standard deviation)

As seen in Table 2, carbon and oxygen are the main components in the wood
surfaces and small amounts of nitrogen and silicon were also detected in both
wood species, whereas calcium was present only in the ash samples.
Nitrogen is present in the form of amine/amide functional groups. This
assignment is as a result of the N1s peak position, which is at approximately 400
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192 Materials Characterisation V


eV (with C-C carbon set at 285.0 eV as the binding energy scale reference). The
presence of such compounds is mainly as a result of naturally occurring proteins
in wood but some contamination by adsorption from the laboratory air cannot be
excluded [8].
From the high resolution spectra (Figure 2b) the functional groups which
made up the C1s spectra have been identified. The C1s spectra of all samples
comprised four peaks with binding energies (BE) of approximately 285.0 (C1),
286.6 (C2), 288.1 (C3) and 289.2 (C4) eV. The C1 carbon component is related
to CC or CH bonds, the C2 carbon component represents single CO bonds,
the C3 carbon component is bonded to a carbonyl or two non-carbonyl oxygen
(C=O or O-C-O) and the C4 class of carbon atoms is bonded to a carbonyl and a
non-carbonyl oxygen (O=C-O) [9].

Figure 2:

XPS survey spectra (a) and high resolution C1s spectra (b) for
interior eucalyptus and ash veneers.

The relative percentages of the C1s components are shown in Table 3


together with the O/C and C1/C2 ratios. The C1 component arises from lignin
and extractives and the C2 component can arise from all wood components but
predominantly from cellulose. For both species, most carbon atoms (6066.5%)
present in the wood surface layer were C1-carbons, and between 29.2 and 33.5%
of the total carbon signal was from the C2 type. According to a normal wood
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composition and the structure of wood components, carbon atoms bonded with
one oxygen atom (C2 component) should be greater. The observed increase in
the presence of C1 components, which was more significant for eucalyptus
samples, might be due to the migration of lipophilic extractives to the wood
surface [9].
Table 3:

Percentages of the C1s spectra components and C1/C2 and O/C


ratios for eucalyptus and ash veneers.

Veneer
Exterior
eucalyptus
Interior
eucalyptus
Exterior ash
Interior ash

C1
66.5
(4.7)
65.4
(2.9)
60.1
(1.7)
60.0
(2.2)

C2
29.2
(3.4)
29.3
(3.2)
32.4
(0.4)
33.5
(2.4)

C3
2.3
(1.6)
2.8
(0.5)
5.0
(1.2)
4.1
(1.0)

C4
2.0
(0.4)
2.8
(0.3)
2.6
(0.1)
2.4
(0.7)

C1/C2

O/C

2.3

0.22

2.2

0.24

1.9

0.27

1.8

0.27

(Standard deviation)

This theory is reinforced by the values obtained for the O/C and C1/C2 ratios,
which are directly related to the chemical composition of wood constituents
(polysaccharides, lignin and extractives). The O/C ratio varied between 0.22 and
0.27 (Table 3). If experimental O/C ratio values are compared to those of pure
compounds, 0.83 for cellulose, 0.33 for lignin and 0.1 for extractives [10] the
preferential presence of lignin and extractives on the wood surface is
demonstrated, mainly in the case of eucalyptus veneers. Moreover, the C1/C2
ratio provides an additional evidence to support the above interpretations.
Theoretically calculated values for the C1/C2 ratio are equal to 0 for pure
cellulose, around 1 for lignin and 10 or higher for extractives [11]. Therefore,
values in the range from 1.8 to 2.3 confirm the presence of extractives on the
wood surfaces and especially on eucalyptus wood.
Finally, when comparing the mean values of the C1/C2 and O/C ratios and
the C1-carbon percentages, more hydrophobic material was found in exterior
eucalyptus veneers. The more hydrophobic character of the eucalyptus wood
samples is in agreement with the results obtained from contact angle
measurements which revealed better wetting properties for ash veneers.
3.3 Time of flight secondary ion mass spectrometry (TOFSIMS)
TOF-SIMS spectra were prepared to represent the masses from 1 to 700 u,
although the range from 100 to 200 u is the most interesting because in this
spectral region fragments of lignin and carbohydrates are detected. On the
contrary, in the region below 100 u, multiple fragments which are common to all
organic materials, the so-called non-specific organic fragments appear and,
therefore, fragments of this region of the spectrum are rarely used in the study of
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194 Materials Characterisation V


organic compounds. Na, Ca or Al, are also detected in the area of the spectrum
below 100 u. However, the intensity of these ions is low when compared with
the intensity of the peaks of hydrocarbons. Extractive organic compounds appear
in areas of the spectrum with m/z values between 230 and 700 u.
Figure 3 shows the comparative positive polarity spectra for ash and
eucalyptus veneers at m/z values from 135 to 185 u. Negative polarity spectra
were nor included due to the low intensity of the observed signals. For both
samples, the characteristic ions of lignin, at m/z =137 and 151 for lignin guaiacyl
units (G), and at m/z=167 and 181 for lignin syringyl units (S), were observed.

Figure 3:

Comparison of the positive ion TOF-SIMS spectra from 135 to 185


u for eucalyptus and ash veneers.

Typical peaks of cellulose and hemicelluloses, localized at m/z = 115, 127,


133 and 145 u, also appeared. Peaks at m/z =115 and 133 u are attributed to
xylan, the peak at 127 u to mannan and the one at 145 u to cellulose. Additional
peaks at m/z =147 and 149 u are attributed to mannan and cellulose.
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Materials Characterisation V

195

TOF-SIMS technique is not quantitative and, therefore, direct comparison of


the intensity of a particular ion in different samples does not allow extracting
conclusions about its abundance. However, it is possible to compare different
samples by referring the intensities of the ions of interest to that of another ion
not related to them. In this way, the intensities of the lignin ions at m/z = 137,
151, 167 and 181 u in eucalyptus and ash wood samples were referred to that of
the ion at m/z =147 u, attributable to hemicelluloses and present in both kind of
samples. The relative intensity of lignin ions in eucalyptus samples was slightly
higher than in the ash ones, which indicated that lignin was more abundant on
the eucalyptus veneer surfaces.
Figure 4 presents the comparison of the positive polarity TOF-SIMS spectra
for eucalyptus and ash veneers in the region from 135 to 450 u. Signals at 383,
397 and 425 u are attributed to organic wood extractives. As shown in the
spectra, the content of extractives is higher in the eucalyptus sample than in the
ash one which is consistent with XPS results.

Figure 4:

Comparison of the positive ion TOF-SIMS spectra from 135 to 450


u for eucalyptus and ash veneers.

Positive ion images for selected ions signals from eucalyptus and ash samples
are shown in Figure 5. Black colour indicates no ion signal and white colour
maximum signal intensity. Images of all the characteristic ions for lignin (137,
151,167 and 181 u) and extractives, mainly sterols (383, 397 and 425 u), are
presented together. Ion images showed that lignin and mainly extractives were
more prominent on eucalyptus than on ash veneer surfaces and, moreover,
revealed that both components were inhomogeneously distributed on the surface.

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196 Materials Characterisation V

Figure 5:

Positive ion images for eucalyptus (a) and ash (b) samples.

3.4 Optic profilometry


Table 4 shows the average values of the roughness parameters Ra (arithmetic
mean of the absolute value of the distances from the mean line to the profile) and
Rq (mean value of the square roots of the distances from the mean line to the
profile) for eucalyptus and ash veneer samples. Due to the heterogeneity of wood
samples, surface roughness values depended strongly on the topographic
characteristics of each particular area, so that the values showed a high
dispersion. Therefore, the most representative roughness values might be those
of the larger areas (called stitch), as the measure itself represents the average of a
larger area of the samples.
The main conclusion drawn from the values of surface roughness is that ash
samples are rougher than eucalyptus samples, approximately 1.7 times based on
the results of the stitch areas, which can be related with the better wettability
behaviour previously encountered.

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Materials Characterisation V

Table 4:

197

Roughness average values for eucalyptus and ash veneer surfaces.

Sample

Magnification
5X (1.2x0.9 mm2)
20X (298x227 m2 )

Eucalyptus
50X (119x91 m2)
STITCH (3x2 mm2)
5X (1.2x0.9 mm2)
20X (298x227 m2 )
Ash
50X (119x91 m2)
STITCH (3x2 mm2)

Ra (m)
11.31
(2.44)
3.44
(1.24)
2.30
(0.91)
15.91
(0.45)
12.17
(1.23)
8.78
(2.60)
6.10
(2.56)
27.38
(2.55)

Rq (m)
16.26
(4.63)
5.11
(0.66)
2.93
(1.00)
23.56
(4.70)
15.92
(1.23)
11.61
(4.14)
8.05
(3.54)
39.36
(6.80)

(Standard deviation)

Acknowledgements
This work was funded by Ministerio de Ciencia e Innovacin, FEDER Funds and
Plan E Fundy (CTQ2009-07539).

References
[1] Bryne, L.E. & Walinder, M.E.P., Ageing of modified wood. Part 1: Wetting
properties of acetylated, furfurylated, and thermally modified wood.
Holzforschung, 64, pp. 295-304, 2010.
[2] Englund F., Bryne L.E., Ernstsson M., Lausmaa J. & Walinder M.,
Spectroscopic studies of surface chemical composition and wettability of
modified wood. Wood Mater. Sci. Eng., 1-2, pp. 8085, 2009.
[3] Bryne, L.O., Lausmaa, J., Ernstsson, M., Englund, F. & Walinder, M.E.P.,
Ageing of modified wood. Part 2: Determination of surface composition of
acetylated, furfurylated, and thermally modified wood by XPS and ToFSIMS. Holzforschung, 64, pp. 305313, 2010.
[4] Tokareva, E.N., Fardim, P., Pranovich, A.V., Fagerholm, H.P., Daniel, G.
& Holmbom, B., Imaging of wood tissue by ToF-SIMS: Critical evaluation
and development of sample preparation techniques. App. Surf. Sci., 253, pp.
75697577, 2007.
[5] Vzquez, G., Gonzlez-Alvarez, J., Santos, J., Freire, M.S. & Antorrena,
G., Evaluation of potential applications for chestnut (Castanea sativa) shell

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[6]

[7]

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and eucalyptus (Eucalyptus globulus) bark extracts. Ind. Crops Prod., 29,
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Nussbaum, R.M., Natural surface inactivation of Scots pine and Norway
spruce evaluated by contact angle measurements. Holz Roh- Werkstoff, 57,
pp. 419-424, 1999.
Christiansen, A.W., Effect of ovendrying of yellow-poplar veneer on
physical properties and bonding. Holz Roh- Werkstof , 52, pp. 139-149,
1994
Popescu, C.N, Tibirna, C.N. & Vasile C., XPS characterization of naturally
aged wood, App. Surf. Sci., 256, pp. 13551360, 2009.
Sinn, G., Reiterer, A. & StanzlTschegg, S.E., Surface analysis of different
wood species using X-ray photoelectron spectroscopy (XPS). J. Mater. Sci.,
36, pp. 4673-4680, 2001.
Barry, A.O., Koran, Z. & Kaliaguine, S., Surface analysis by ESCA of
sulfite post-treated CTMP. J. Applied Polym. Sci., 39, pp. 3142, 1990.
Sernek, M., Kamke1, F.A. & Glasser, W.G., Comparative analysis of
inactivated wood surface, Holzforschung, 58, pp. 2231, 2004.

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Materials Characterisation V

199

Interface resistances in heat and moisture


transport: semi-scale experimental analysis
Z. Pavlk, J. Mihulka, J. umr, M. Pavlkov & R. ern
Department of Materials Engineering and Chemistry,
Faculty of Civil Engineering, Czech Technical University in Prague,
Czech Republic

Abstract
A sophisticated semi-scale system which allows experimental simulation of heat
and moisture transport in building structures is employed for analyzing heat and
moisture transfer across interfaces in stone masonry formed by argillite walling
blocks and lime-pozzolana mortar. The dimensions of investigated structure are
close to a real wall but the measuring accuracy is the same as in a laboratory
experiment. Combined relative humidity and temperature mini-sensors are
utilized in continuous long-term monitoring. Measured temperature and relative
humidity profiles provide information on the properties of the interface between
the walling material and mortar which makes possible to identify the interface
permeability. This parameter can then be used in computational models of heat
and moisture transport in masonry which adds to the accuracy of model
predictions.
Keywords: heat and moisture transport, interface resistances, semi-scale
experiment, stone masonry, argillite, lime-pozzolana mortar.

1 Introduction
Computational modelling of coupled moisture and heat transport represents an
effective tool for prediction of behaviour of building structures exposed to
climatic load. For reliability of computational analysis, two requirements must
be met. At first, mathematical-physical model describing the coupled moisture
and heat transport must be formulated. From the theoretical point of view, this
model should be sufficiently sophisticated and complex, and should take into
account all the external and internal effects that affect the moisture and heat
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200 Materials Characterisation V


transport. Typical example of such complex models represents for instance
hybrid model developed by Grunewald [1, 2] that takes into account both
diffusion and convection effects on moisture and heat transport. Although these
models describe the physical reality of coupled moisture and transport in
sophisticated way, their practical application for hygrothermal analysis of
building structures is often limited by the accuracy and availability of input
parameters that represent the second limiting requirement of computational
modelling.
There are two types of input parameters which have to be known in advance
for precise computational analysis. The first are initial and boundary conditions.
In case of analysis of existing structure, for example by reason of intended
reconstruction, initial conditions can be determined using on site analysis of
moisture and temperature fields in the studied structure. Boundary conditions are
of two types. The first of them are meteorological data for temperatures, relative
humidities, rainfall and solar radiation, possibly also concentration of acidforming gases in the atmosphere. This type of data can be obtained from
meteorologists in the form of so-called TRY (Test Reference Year) data which
present certain average values over a sufficiently long time period. The second
type of boundary conditions involves water content in the underground soil close
to the studied building. These data can be obtained again by on site analysis [3].
The second type of input parameters are hygric and thermal transport and
storage parameters of the materials of the structure which appear in water and
heat mass balance equations implemented in the models. In case of study of
coupled moisture and heat transport, these parameters include moisture
diffusivity and diffusion coefficient of water vapour, sorption isotherms and
water retention curves that can be optionally expressed as moisture potential
curves, thermal conductivity and specific heat capacity. Within the application of
computational modelling, one must take into account that all above given
parameters are functions of both temperature and moisture. Therefore, there is a
need to determine these parameters in dependence on moisture and temperature
changes what is highly time-consuming, and for some types of materials
practically unfeasible. On that account, one must assume diversion of
computational simulations from reality, and the computer codes must be
calibrated and validated using experimentally measured moisture and moisture
profiles. Only after this validation is done, the computational modelling can be
applied with sufficient accuracy.
Specific problem for validation of computational codes solving the coupled
moisture and heat transport represent composite materials and structures, where
interface resistances crucially affect the reliability of modelling. Most classical
models of heat and moisture transport in porous materials do not deal with
moisture transport across interfaces between two porous materials in an explicit
way. In practical calculations, the simplest solution is commonly used. It is
assumed that there is ideal contact between the two materials, which means the
equality of temperatures and moistures, taken as limits on the right and the left to
the interface. However, this requirement can sometimes lead to dramatic but
unclear moisture profiles in the regions close to the interface, particularly if the
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Materials Characterisation V

201

bordering materials have considerably different transfer coefficients. Therefore,


the condition that the macroscopic capillary pressure must be continuous across
the interface is adopted in more sophisticated models, implying an ideal
hydraulic contact. Then, at the interface between two different materials a
moisture jump across the interface appears, which can be theoretically
determined on the basis of the measured water accumulation functions of both
materials. In the case a non-ideal hydraulic contact is formed on the interface due
to the different pore size distributions of the adjacent porous materials, a jump of
capillary pressure along the interface characterized by the interface permeability
can appear. Typical example of non-ideal hydraulic contact of two materials
represent masonry, where the water transport properties of walling blocks and
mortar are different due to the differences in their pore size distribution. In order
to decide which of the particular transport models is realistic for a specific
interface, an experimental analysis is required.
On that account, an experimental analysis of temperature and moisture
transport across the material interfaces in stone masonry is studied in this paper
to reveal the interface effects on the moisture and temperature distribution.

2 Semi-scale experiments
The semi-scale experiments are presently very popular in verification and
calibration of HAM (Heat, Air, and Moisture transport) models since they allow
monitoring of hygrothermal changes in the studied structures in more detailed
way and the certain specific cases can be studied what is not very common in the
case of full test house measurement [4, 5].
The semi-scale measuring system for determination of temperature and
moisture fields is designed in such a way that it simulates conditions, which are
as close as possible to the real conditions on building site, but it still maintains its
laboratory character, so that the expenses are kept considerably lower compared
to a real test house. Also the accuracy of applied measuring methods for
moisture content and temperature measurement is much higher compared to insitu measurements [6].

3 Experimental
Within the performed experiments, the moisture and heat transport in the fragment
of argillite wall was studied. Two separate semi-scale experiments were designed
and performed in order to evaluate the effect of interface resistances on the
transition between the argillite walling blocks and mortar. Within the first
experiment, the heat transport was simulated, whereas the relative humidity was
maintained on constant level. In the second experimental arrangement, relative
humidity transport was monitored at constant temperature conditions.
3.1 Studied masonry and inbuilt materials
Two materials typical for historical masonry in Central European territory were
used. The researched fragment of the stone masonry consisted of argillite blocks
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202 Materials Characterisation V


and lime mortar with pozzolana admixture based on calcined kaoline mixed with
milled mudstone. The composition of applied mortar is given in Table 1.
Table 1:
lime hydrate
(kg)
200

Composition of applied plaster.


pozzolana
(kg)
50

sand 0 4 mm
(kg)
750

w/d ratio
(-)
0.23

In Table 1, w/d represents the water/dry substance ratio. Lime hydrate is


product of lime kiln ertovy schody, Inc., Czech Republic, whereas the silicious
sand is coming from sand-pit Hlavaov, Czech Republic. The applied argillite is
coming from quarry Dbn, Czech Republic. It is highly heterogeneous fine-pore
material with anisotropic structure. It is characteristic by diversity in
composition, whereas its main constituents are illite, kaolin, minerals of SiO2,
spar and mica.
Basic physical properties of both masonry materials are given in Table 2.
Table 2:
material
mortar
argillite

Basic properties of masonry materials.

bulk density
(kg/m3)
1688
1353

matrix density
(kg/m3)
2560
2235

total open porosity


(-)
0.34
0.39

3.2 Experimental arrangement, measuring technology


For simulation of moisture and heat transport in the investigated structure, a
semi-scale system was used. The device (Figure 1) consists of two climatic
chambers for simulation of climatic conditions, connecting tunnel, where the
investigated structure is placed, and commercial devices for continuous
monitoring of field variables as relative humidity, temperature, liquid moisture
content, salinity, heat flux, etc. It is also equipped with optional sprinkling
device for rainfall simulation.
In the presented experiments, monitoring of relative humidity and
temperature changes in the specific places of studied structure was done. For this
purpose, sophisticated technique from Ahlborn was used. The accuracy of
particular sensors was as follows: 2% for capacitive relative humidity sensors
applicable in the range of humidities 5-98%, for temperature sensors 0.4C in
the temperature range from 20C to 0C and 0.1C in the range from 0C to
70 C. For testing the tightness of climatic chamber system, the anemometers for
air flow velocity measurements were used. The whole measuring system was
operated by a computer, including the climatic data entry into the particular
climatic chambers. The details on the system including the measuring technology
and sensors calibration can be found in [6].
The measuring process can be divided into several basic phases: walling the
investigated structure, sensors installation into the built wall fragment, sample
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Materials Characterisation V

Figure 1:

203

Climatic chamber system for semi-scale experiments.

positioning into the tunnel between the climatic chambers, climatic loading
simulation, temperature and relative humidity monitoring, data evaluation. The
walling of the studied structure was done in the standard way using dry mortar
mix and wet technological process. The sensors for monitoring temperature and
relative humidity were placed to the investigated construction to beforehand
bored holes. The upper part of the bore opening was closed by silicon sealing.
Placing of the sensors was done regarding to the study of interface moisture and
heat transport (Figure 2).
For a proper setting of climatic conditions, it was necessary to achieve nearsteady-state conditions in the studied wall. Therefore, there was necessary to dry
freshly built wall to remove technological water. The drying was done at 50C
and 10% of relative humidity for one month.
After that, the first experiment simulating the heat transport at constant
moisture conditions was started. On one side of the studied wall, constant
temperature of -9.5C was maintained, whereas on the other side of the masonry
fragment, constant temperature of 25C was simulated. The relative humidity
varied during the experiment in the range of 10%, typically between 40 and
50% in respect to performance of climatic chambers. Duration of the first
experiment was 84 days.

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204 Materials Characterisation V

Figure 2:

Sensors positioning and wall arrangement (dimensions in mm).

The second experiment was designed to simulate gaseous moisture transport


without temperature effects. Also in this case, the climatic chambers parameters
were limiting factor. On one side of the wall, relative humidity of 45% was
simulated, whereas on the opposite wall side, 95% was reached. The temperature
varied within the range of 25 to 28C. Duration of this experiment was 81 days.

4 Results and discussion


The temperature profiles measured in the first semi-scale experiment are shown
in Figures 36. The results are presented in two cross sections (A-A, B-B),
according to the scheme in Figure 2.
The measured temperature profiles in Figures 36 are more or less linear.
This indicates that steady state heat transport was reached. We can also observe
the expected jumps in temperatures at the contacts of measured wall with
ambient environment. They are caused by thermal resistances between the
material surface and ambient air. The thermal resistances between the argillite
blocks and mortar are manifested as well. The effects of interface resistances are
not so distinct as the surface resistances as solid-solid heat transfer can be
generally realized in a more ideal way than solid-gas transfer. Nevertheless, their
significance is perceptible.
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Materials Characterisation V

Figure 3:

Figure 4:

205

Temperature profiles in cross section A-A (first experiment).

Temperature profiles in cross section A-A (end of the first


experiment).

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206 Materials Characterisation V

Figure 5:

Figure 6:

Temperature profiles in cross section B-B (first experiment).

Temperature profiles in cross section B-B (end of the first


experiment).

The relative profiles measured in the second semi-scale experiment are shown
in Figures 7 and 8.

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Materials Characterisation V

207

Figure 7:

Relative humidity profiles in cross section A-A (second


experiment).

Figure 8:

Relative humidity profiles in cross section B-B (second


experiment).

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208 Materials Characterisation V


Apparently, in case of simulation of water vapour transport, similar features
as in heat transport simulation are observed. The experimental relative humidity
profiles reveal significant effects of interface resistances on gaseous moisture
transport at the contact of argillite blocks and mortar. The surface resistances
remarkably affect the water vapour distribution in the studied masonry as well.
The steep parts of relative humidity profiles are highly important for calibration
and validation of HAM models of transport phenomena in multilayered systems.
For demonstration of temperature conditions within the water vapour
transport simulation, Figure 9 is introduced. Clearly, the effect of interface
resistances in the stone-mortar-stone transition zone and surface resistances can
be observed even in the case of low temperature differences on opposite wall
sides.

transition
zone

Figure 9:

Temperature distribution in cross section B-B (second experiment).

5 Conclusions
Experimental investigation of water vapour and heat transport across the
interfaces in stone masonry was done in the conditions of 1-D semi-scale
experiment. The climatic loading of the studied structure was chosen in such a
way that water vapour transport under isothermal conditions and heat transport at
constant relative humidity were simulated. The data obtained in both
experiments confirmed the significant effect of both interface and surface
resistances on water vapour and heat propagation, thus the necessity to include
these effects in computational modelling of coupled moisture and heat transport.
On the basis of measured data, determination of heat and water vapour
resistances between particular materials layers is possible using methods of
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Materials Characterisation V

209

inverse analysis. Also, the surface resistances on the contact of studied building
structure with ambient air can be accessed. In this way, the results can contribute
to higher accuracy of future computational modelling. Neglecting the behaviour
of the transition zone between the particular materials forming stone masonry
structures, on the other hand, may lead to possible improper design of renovation
or construction solutions and subsequent material and structural damage.

Acknowledgement
This research has been supported by the Czech Ministry of Education, Youth and
Sports, under project No MSM 6840770031.

References
[1] Grunewald, J., Diffusiver und konvektiver Stoff- und Energietransport in
kapillarporsen Baustoffen, Ph.D. Thesis, TU Dresden, Dresden, 1997.
[2] ern, R. & Rovnankov, P., Transport Processes in Concrete, 1st ed.,
Spon Press: London, 547 pp., 2002.
[3] Pavlk, Z., Michlek, P., Pavlkov, M., Kopeck, I., Maxov, I. & ern,
R., Water and Salt Transport and Storage Properties of Men Sandstone.
Construction and Building Materials, 22(22), pp. 1736-1748, 2008.
[4] Krus, M., Rsler, D. & Sedlbauer, K., New model for the hygrothermal
calculation of condensate on the external building surface. Research in
Building Physics and Building Engineering, Fazio, Ge, Rao, Desmarais
(eds.), Taylor & Francis Group, London, pp. 329-333, 2006.
[5] Pavlk, Z., Mihulka, J., umr, J. & ern, R., Experimental monitoring of
moisture transfer across interfaces in brick masonry. Structural Faults and
Repair 2010 [CD-ROM], Engineering Technics Press Edinburgh,
Edinburgh, 2010.
[6] Pavlk, Z., Pavlk, J., Jiikov, M. & ern, R., System for Testing the
Hygrothermal Performance of Multi-Layered Building Envelopes. Journal
of Thermal Envelope & Building Science, 25(1), pp. 239-249, 2002.

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Section 6
Mechanical
characterisation
and testing

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Materials Characterisation V

213

Tension/compression test of auto-body


steel sheets with the variation of the pre-strain
and the strain rate
G. H. Bae & H. Huh
School of Mechanical, Aerospace and Systems Engineering, KAIST,
Republic of Korea

Abstract
This paper investigates the tension/compression hardening behaviour of autobody steel sheets with the variation of the pre-strain and the strain rate. To
conduct tension/compression tests with the variation of the pre-strain and the
strain rate, an experimental method was established by using a newly developed
clamping device to suppress buckling of a specimen. The clamping device
provides the supporting force from compression-type coil springs during the test
with a conventional dynamic material fatigue testing machine. From
experiments, the tension/compression hardening behaviour was observed with
the variation of the pre-strain and the strain rate. Effects of the pre-strain and the
strain rate on the hardening behaviour were also investigated based on the
tension/compression test results.
Keywords: tension/compression test, clamping device, pre-strain, strain rate.

1 Introduction
Spring-back caused by the elastic recovery of the residual stress inside a formed
part has been one of the most significant sources of defects in the sheet metal
forming process in recent years. Spring-back predictability of numerical
simulation, however, has not been satisfactory because its performance is not
good enough to calculate accurate residual stress during the forming process. To
improve spring-back predictability in numerical simulation, many researchers
have been trying to use accurate information of the hardening behaviour of sheet
materials in finite element analysis. The hardening behaviour of sheet materials

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doi:10.2495/MC110191

214 Materials Characterisation V


has been measured with various mechanical testing methods in the quasi-static
region [13]. It has been successful to predict spring-back accurately with
numerical simulation by applying the precise hardening behaviour obtained from
tension/compression tests at the quasi-static state [4, 5].
Numerical simulation still cannot accurately predict the final shape of the
formed part after spring-back for a higher strain rate because of lack in
information about the tension/compression hardening behaviour at high strain
rates. To enhance spring-back predictability in numerical simulation for actual
formed parts, the accurate hardening behaviour should be applied in finite
element analysis by performing tension/compression tests with the variation of
the strain rate as well as of the pre-strain.
This paper investigates the tension/compression hardening behaviour of autobody steel sheets with the variation of the pre-strain and the strain rate. To
conduct tension/compression tests, a simple clamping device was newly
developed to suppress buckling of a specimen during the compression loading.
The clamping device provides the side force from compression-type coil springs.
The compression-type coil springs were selected for the desired clamping
pressure calculated by the plate buckling theory adopted by Cao and Wang [6].
Based on the secant formula and the Euler method adopted by Boger et al. [2],
specimen dimensions were also designed to prevent buckling along the width
direction in the gauge section and along the longitudinal direction in the
unclamped region. The strain in the gauge region of the specimen was measured
directly by the digital image processing technique. The hardening behaviour of
auto-body steel sheets was investigated precisely based on the
tension/compression test results with the variation of the pre-strain and the strain
rate.

2 Test preparation
To obtain a larger compressive strain range in the tension/compression test,
buckling of a specimen should be prevented by using a properly-designed
specimen and by imposing a sufficient clamping force. Fig. 1 shows three
representative buckling modes in the tension/compression test: (1) buckling in
the thickness direction in the gauge region (T-buckling); (2) buckling in the

Figure 1:

Three representative buckling modes in the tension/compression


test.

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Materials Characterisation V

215

unclamped region (L-buckling); (3) buckling in the width direction in the gauge
region (W-buckling). T-buckling mode can be suppressed by imposing a
sufficient clamping force on a specimen with a special clamping device. Lbuckling and W-buckling modes can be prevented by designing an appropriate
specimen shape.
2.1 Specimen shape
Boger et al. [2] used the secant formula and the Euler method to calculate the
attainable compressive strain for L-buckling and W-buckling modes,
respectively. When the flow curve is expressed by the Swift model, the
attainable compressive strain for two buckling modes can be calculated as
follows:
1

B n

eL = e0 -1
W

(1)
eW =

p 2 nW 2
- e0
3G 2

(2)

where B and W are the specimen width in the gripping region and the gauge
region, respectively. G is the gauge length of the specimen. 0 and n are the
plastic strain for the yield stress and the hardening exponent in the Swift model,
respectively. If the gauge length of the specimen and the coefficients of the Swift
model are given, the attainable compressive strains are a function of the gauge
width. More detailed formulation procedure can be found in the reference [2].
The specimen design was performed using the above equations formulated for
the attainable compressive strain of L-buckling and W-buckling. The selected
steel sheets are SPCC and DP590 which are commonly used auto-body steel
sheets. Strains at uniform elongation before necking initiates are approximately
0.15 and 0.12 for SPCC and DP590, respectively. These values are assigned as
the maximum pre-strain for tension/compression tests without necking of a
specimen. Table 1 shows the coefficients of the Swift model and r-values for
SPCC and DP590 at a quasi-static state. A specimen shape for the uniaxial
tensile test [7, 8] was utilized as reference specimen dimensions for
tension/compression tests as shown in fig. 3(a). In order to reduce the required
clamping force to suppress T-buckling, the gauge length is first reduced from 30
mm to 20 mm. The small clamping force is favourable for the reliable
tension/compression test, which can reduce the frictional and biaxial effect on a
specimen. The attainable compressive strain was plotted with respect to the
gauge width as shown in fig. 2. From the plotted curves, the optimal gauge width
can be selected as 8.8 mm for SPCC and 8.2 mm for DP590, respectively. To
ensure a stable testing region for the two steel sheets, the final gauge width can
be determined to be 8.8 mm as shown in fig. 3(b).

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216 Materials Characterisation V


Table 1:

Coefficients of the Swift model and r-values of SPCC and DP590.


K [MPa]

r0

r45

r90

SPCC

555.772

0.01121

0.253

1.381

1.094

1.697

1.317

DP590

1079.261

0.00879

0.220

0.704

0.784

0.948

0.805

Attainable compressive strain

Material

0.4

L-buckling
SPCC
DP590

0.3

W-buckling
SPCC
DP590

0.2

SPCC, 0.15
DP590, 0.12

0.1
0.0

10

15

20

25

Width of the gauge region [mm]

Figure 2:

Attainable compressive strain with respect to the width at the gauge


region for SPCC and DP590.

(a)

(b)
Figure 3:

Specimen dimensions for the uniaxial tensile test and the


tension/compression test: (a) uniaxial tension test [7, 8]; (b)
tension/compression test (suggested).

2.2 Clamping force


Cao and Wang [6] proposed an equation to calculate the blank holding force to
suppress flange wrinkling in the sheet metal forming process. To calculate the
clamping force to suppress T-buckling of a specimen, the plate buckling theory
was also employed by assuming the gauge region of a specimen to be a
rectangular plate model. The critical normal force required to suppress buckling
of a specimen can be calculated by
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Materials Characterisation V
n +1

2u x

e
ln
1

G
3KGWt

F=

n +1
n
4(n + 1)d 2 ct

1
t
t
1

- G 2 + e0 m 2 d + 2 m 2 d + 2 tan (md )

217

(3)

2u x ( l - u x )
2p
,d=
G
2
u
p
1+ 2R
x
where t and ux are the thickness of a specimen and a certain edge displacement.
K, n and 0 are coefficients of the Swift model. For the tension/compression test,
the specimen thickness and width change in the gauge region during
deformation. These values can be calculated based on anisotropy of material.
where c =

1+ R

, m=

W = W0 -

t = t0 -

2u
W0
ln 1- x
1 + R
G

(4)

t0 R 2ux
ln 1
1 + R
G

(5)

The critical normal force defined in eqn. (3) is now used to calculate the
critical clamping force to suppress T-buckling in the tension/compression test.
More detailed formulation procedure of the critical normal force can be found in
the reference [6]. Fig. 4 shows the critical clamping force with respect to the
compressive plastic strain. From the plotted curves, the required clamping force
for SPCC and DP590 can be determined to be 2.003 kN and 2.275 kN,
respectively.

Clamping force [kN]

10

G20W8.8
SPCC
8
DP590

DP590
0.12

SPCC
0.15

6
4
2
0
0.00

0.05

0.10

0.15

0.20

Compressive strain

Figure 4:

Required clamping force with respect to the compressive strain for


SPCC and DP590.

2.3 Design of a new clamping device


Based on specimen dimensions and the required clamping force, a new clamping
device was developed to suppress T-buckling of specimens. Fig. 5(a) gives a
schematic diagram for the clamping device developed. A controllable clamping
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218 Materials Characterisation V


system was suggested by using compression-type coil springs. Four coil springs on
each side compress a specimen by fastening the bolts up to the desired deflection
distance which is determined by the gap controlling bar. Before the
tension/compression test starts, the gap controlling bar is uninstalled from the
clamping device in order to allow thickness change of the specimen during the
tension/compression test. For lubrication between the specimen and the clamping
plate, a Teflon film (3M 5490 model) with a thickness of 0.09 mm is attached on
the clamping plate. A compression-type coil spring was selected based on the
clamping force calculated in Section 2.2 for SPCC and DP590. The maximum
clamping force was selected at 4 kN to ensure performance of the device although
the required clamping forces were 2.003 kN for SPCC and 2.275 kN for DP590.
To provide the required clamping forces, 16L40 coil spring was selected for
the clamping device. The maximum load and the spring constant of the selected
coil spring are 1.265 kN and 0.158 kN/mm, respectively.
The clamping device was manufactured with the specified dimensions based
on the specimen shape and the spring size. As shown in fig. 5(b), the springloaded clamping device has a small and simple structure with light weight. The
clamping force is controllable by determining the deflection distance of the coil
springs. These advantages are favourable for easy and convenient
tension/compression tests at high strain rates.
Specimen
Teflon film

Coil springs
Gap controlling bar

Bolt

Nut

Clamping plate

Compression plate

(a)
Figure 5:

(b)

Spring-loaded clamping device for the tension/compression test: (a)


schematic diagram; (b) manufactured clamping device.

3 Experiments
3.1 Test material
The tension/compression test of auto-body steel sheets was conducted with the
variation of the pre-strain and the strain rate. Test materials were SPCC and
DP590 with a thickness of 1.2 mm. The chemical composition of the sheet
metals is presented in table 2.
Table 2:
Material
SPCC
DP590

Chemical composition of SPCC and DP590 [wt.%].


C
0.085
0.326

Mn
0.420
1.700

Si
0.040
0.123

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P
0.0012
0.0162

S
0.0150
0.0009

Materials Characterisation V

219

3.2 Testing machine


A clamped specimen is gripped by the dynamic material fatigue testing machine,
INSTRON8801, to perform tension/compression tests with the variation of the
pre-strain and the strain rate. The dynamic material fatigue testing machine
shown in fig. 6 has a maximum stroke of 75 mm in the vertical direction
actuated by a hydraulic system. The load cell installed in the testing machine can
measure a load of up to 100 kN. The gripper is also actuated by a hydraulic
system.

Figure 6:

Tension/compression testing system utilizing the dynamic material


fatigue testing machine, INSTRON8801, and the spring-loaded
clamping device.

True strain in the T/C test

0.15

Actuator displacement: 3 mm
Strain rate: 0.001 /sec

0.10

0.05
SPCC
DP590
0.00

Total actuator movement [mm]

(a)
Figure 7:

(b)

Strain measuring method using the digital image processing


technique with the high speed camera: (a) recording of the
deformation history; (b) measured strain during the
tension/compression test.

3.3 Strain measurement


Because the specimen is fully covered by the clamping plates, conventional
extensometers cannot be employed to measure the strain in the side of the gauge
region during the tension/compression test. As an alternative, a digital image
processing technique was utilized to measure the strain directly. Before the
tension/compression test, a speckled pattern was sprayed on the side wall of the
specimen as shown in fig. 7(a). A high speed camera captures a series of frames
for deformation during the tension/compression test. The strain can be measured
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220 Materials Characterisation V


from a graph in fig. 7(b) obtained by analyzing recorded frames using the digital
image processing technique.
3.4 Tension/compression test
Stable tension/compression testing conditions were established by comparing the
response of the testing machine with the variation of the actuator displacement
and the strain rate. Table 3 presents experimental conditions for the tension
/compression test. From the experiments, load-displacement curves and strains in
the gauge region were determined for various pre-strains and strain rates. The
tension/compression hardening curves can be obtained after correction
procedures to subtract the frictional and biaxial effects induced by the clamping
force.
Table 3:

Material

SPCC

DP590

Experimental table for tension/compression tests of SPCC and


DP590.
Displacement
[mm]
1.0
2.0
3.0
4.0
1.0
2.0
3.0

0.001
O
O
O
O
O
O
O

Strain rate [/sec]


0.01
0.1
O
O
O
O
O
O
O
O
O
O
O
O
O
O

1.0
X
X
O
O
X
X
O

3.5 Correction of acquired load


All acquired stressstrain results require corrections for frictional and biaxial
effects induced by the clamping force, Fc , because the specimen is compressed
by the spring-loaded clamping device in the thickness direction to suppress
T-buckling. The measured force from the load cell, Fm , is the addition of the
force from the specimen deformation, Fd , and the frictional force, Ff .

Fd = Fm - Ff

(6)

The friction behaviour is represented by the Coulomb friction law as follows


[1, 2]:

Ff = m Fc

(7)

The frictional conditions can be changed according to the material, the


geometrical change of a specimen and the accumulated damage to the Teflon
film. The friction coefficient is generally known to be in the range of 0.03~0.09
when the Teflon film is used for tension/compression tests [24]. The friction
coefficients for SPCC and DP590 are selected as 0.06 and 0.08, respectively, to
correct the acquired curve obtained from the tensile test with clamped into a
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Materials Characterisation V

221

corrected curve by comparison with the acquired curve obtained from a tensile
test with unclamped.
In order to subtract the through-thickness stress, t , induced by the clamping
force, the von Mises yield function is utilized to calculate the effective stress
corrected from the biaxial effect.

1
2
(sm - st ) + sm2 + st2

s=

(8)

where m is the measured stress from the load cell. After both frictional and
biaxial corrections, the flow curve of the clamped specimen agrees well with that
of the unclamped specimen as shown in fig. 8.

400

SPCC

1000

Strain rate = 0.001 /sec


Clamping force = 2.003 kN
= 0.06

300
200
Acquired curve (unclamped)
Acquired curve (clamped)
Corrected curve

100
0
0.00

0.05

0.10

True stress [MPa]

True stress [MPa]

500

800

DP590
Strain rate = 0.001 /sec
Clamping force = 2.275 kN
= 0.08

600
400
Acquired curve (unclamped)
Acquired curve (clamped)
Corrected curve

200
0
0.00

0.15

0.05

True strain

(a)
Figure 8:

Frictional and biaxial corrections in the uniaxial tension state: (a)


SPCC, 0.001/sec; (b) DP590, 0.001/sec.
500

SPCC, 0.001 /sec

250

Simple tension
Displacement (pre-strain)
1 mm (0.040)
2 mm (0.080)
3 mm (0.120)
4 mm (0.162)

0
-250
-500
0.00

0.05

0.10

0.15

SPCC, 0.01 /sec

250

Simple tension
Displacement (pre-strain)
1 mm (0.037)
2 mm (0.075)
3 mm (0.114)
4 mm (0.156)

0
-250
-500
0.00

0.20

0.05

True strain

Simple tension
Displacement (pre-strain)
1 mm (0.038)
2 mm (0.077)
3 mm (0.118)
4 mm (0.161)

0
-250

0.10

0.15

True strain

0.20

SPCC, 1.0 /sec

250

Simple tension
Displacement (pre-strain)
3 mm (0.116)
4 mm (0.159)

0
-250
-500
0.00

0.05

0.10

0.15

0.20

True strain

(c)
Figure 9:

0.20

True stress [MPa]

True stress [MPa]

SPCC, 0.1 /sec

0.05

0.15

(b)
500

250

-500
0.00

0.10
True strain

(a)
500

0.15

(b)

True stress [MPa]

True stress [MPa]

500

0.10

True strain

(d)

Tension/compression test results of SPCC at various strain rates:


(a) 0.001/sec; (b) 0.01/sec; (c) 0.1/sec; (d) 1.0/sec.

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222 Materials Characterisation V


1000

DP590, 0.001 /sec

500

Simple tension
Displacement (pre-strain)
1 mm (0.032)
2 mm (0.070)
3 mm (0.112)

0
-500
-1000
0.00

0.05

0.10

True stress [MPa]

True stress [MPa]

1000

DP590, 0.01 /sec

500

Simple tension
Displacement (pre-strain)
1 mm (0.034)
2 mm (0.073)
3 mm (0.118)

0
-500
-1000
0.00

0.15

0.05

True strain

(a)
DP590, 0.1 /sec

500

Simple tension
Displacement (pre-strain)
1 mm (0.029)
2 mm (0.066)
3 mm (0.109)

0
-500
-1000
0.00

0.05

0.10

DP590, 1.0 /sec

500

Simple tension
Displacement (pre-strain)
3 mm (0.106)

0
-500
-1000
0.00

0.15

0.05

True strain

Tension/compression test results of DP590 at various strain rates:


(a) 0.001/sec; (b) 0.01/sec; (c) 0.1/sec; (d) 1.0/sec.
500

SPCC, 1 mm

250

Strain rate [/sec]


0.1
0.01
0.001

0
-250
-500
0.00

0.05

0.10

0.15

SPCC, 2 mm

250

Strain rate [/sec]


0.1
0.01
0.001

0
-250
-500
0.00

0.20

0.05

True strain

Strain rate [/sec]


1.0
0.1
0.01
0.001

0
-250

0.10

0.15

0.20

True stress [MPa]

True stress [MPa]

250

0.05

0.20

SPCC, 4 mm

250

Strain rate [/sec]


1.0
0.1
0.01
0.001

0
-250
-500
0.00

0.05

True strain

(c)
Figure 11:

0.15

(b)
500

SPCC, 3 mm

-500
0.00

0.10
True strain

(a)
500

0.15

(d)

True stress [MPa]

True stress [MPa]

500

0.10

True strain

(c)
Figure 10:

0.15

(b)
1000
True stress [MPa]

True stress [MPa]

1000

0.10

True strain

0.10

0.15

0.20

True strain

(d)

Tension/compression test results of SPCC at various actuator


displacements (pre-strains): (a) 0.001/sec; (b) 0.01/sec; (c) 0.1/sec;
(d) 1.0/sec.

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Materials Characterisation V

1000

DP590, 1 mm

500

Strain rate [/sec]


0.1
0.01
0.001

0
-500
-1000
0.00

0.05

0.10

True stress [MPa]

True stress [MPa]

1000

DP590, 2 mm

500

Strain rate [/sec]


0.1
0.01
0.001

0
-500
-1000
0.00

0.15

0.05

True strain

0.10

0.15

True strain

(a)

(b)

1000
True stress [MPa]

223

DP590, 3 mm

500

Strain rate [/sec]


1.0
0.1
0.01
0.001

0
-500
-1000
0.00

0.05

0.10

0.15

True strain

(c)
Figure 12:

Tension/compression test results of DP590 at various actuator


displacements (pre-strains): (a) 0.001/sec; (b) 0.01/sec; (c) 0.1/sec.

4 Hardening behaviour
True stresstrue strain curves were obtained after frictional and biaxial
corrections, as shown in figs. 9 and 10. Hardening curves expand with the
increase of the pre-strain at various strain rates. To investigate the strain rate
effect on the hardening behaviour, true stresstrue strain curves were redrawn
with the variation of the strain rate as shown in figs. 11 and 12. Hardening curves
also expand with the increase of the strain rate at various pre-strains. It is well
known that the strain and the strain-rate hardening are caused by micro-structure
changes inside the materials. To confirm this general expectation, Huh et al. [9]
demonstrated by observing TEM experimental results that the mechanism of the
strain-rate hardening is the change of the dislocation structures and the increase of
the dislocation density. The mechanism of the hardening behaviour during
tension/compression loading also can be explained by the micro-structure change
of steel sheets caused by the pre-strain and the strain rate effect. From the
experiments, it is clear that the tension/compression hardening behaviour is
changed by the strain rate as well as by the pre-strain. This means that the prestrain and the strain rate effect on the tension/compression hardening behaviour
should be considered simultaneously to improve spring-back predictability in
numerical sheet metal forming simulation.

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224 Materials Characterisation V

5 Conclusions
This paper investigates tension/compression hardening behaviour by performing
tension/compression tests using a newly developed spring-loaded clamping
device. Contributions in this paper are summarized as follows:
1) A specimen shape was designed with the secant formula and the Euler
method adopted by Boger et al. [2] to prevent L-buckling and W-buckling in the
desired tension/compression test range. The clamping force to suppress Tbuckling was calculated with the plate buckling theory. A spring-loaded
clamping device was newly developed to suppress T-buckling in the
tension/compression test. From experiments, it is noted that the dimension of a
specimen and the choice of compression-type coil springs are appropriate to
execute reliable tension/compression tests.
2) The strain in the gauge region of a clamped specimen was measured
directly by using a digital image processing technique in order to overcome the
inherent structural problems in the use of conventional contact-type
extensometers. The measuring scheme using the digital image processing
technique can provide accurate strain history in the gauge region of a clamped
specimen during tension/compression tests.
3) With the test conditions established, hardening curves were reliably
obtained for various pre-strains and strain rates. The tension/compression
hardening curves were expanded with the increase of the strain rate as well as
with the increase of the pre-strain. The mechanism of the pre-strain and strain
rate hardening was explained by micro-structure changes, such as dislocation
structures and dislocation density. Experiments provide good information of the
hardening behaviour with respect to the pre-strain and the strain rate.
4) The newly developed clamping device can be directly applied to
tension/compression tests at high strain rates because of its compactness and
convenience to control the clamping force with various tensile testing machines.
This device guarantees the response of the clamping pressure in real time when
the clamping condition is changed by the specimen deformation during
tension/compression tests.

References
[1] Lee, M. G., Kim, D., Kim, C., Wenner, M. L., Wagoner, R. H. & Chung, K.,
Springback evaluation of automotive sheets based on isotropickinematic
hardening laws and nonquadratic anisotropic yield functions, part II:
characterization of material properties. Int. J. Plast., 21, pp. 883914, 2005.
[2] Boger, R. K., Wagoner, R. H., Barlat, F., Lee, M.G. & Chung, K.,
Continuous, large strain, tensioncompression testing of sheet material. Int.
J. Plast., 21, pp. 23192343, 2005.
[3] Cao, J., Lee, W., Cheng, H. S., Seniw, M., Wang, H. P. & Chung, K.,
Experimental and numerical investigation of combined isotropickinematic
hardening behavior of sheet metals. Int. J. Plast., 25, pp. 942972, 2009.

WIT Transactions on Engineering Sciences, Vol 72, 2011 WIT Press


www.witpress.com, ISSN 1743-3533 (on-line)

Materials Characterisation V

225

[4] Lee, M. G., Kim, D., Kim, C., Wenner, M. L. & Chung, K., Springback
evaluation of automotive sheets based on isotropickinematic hardening
laws and nonquadratic anisotropic yield functions. part III: applications.
Int. J. Plast., 21, pp. 915953, 2005.
[5] Taherizadeh, A., Ghaei, A., Green, D. E. & Altenhof, W. J., Finite element
simulation of springback for a channel draw process with drawbead using
different hardening models. Int. J. Mech. Sci., 51, pp. 314325, 2009.
[6] Cao, J. & Wang, X., An analytical model for plate wrinkling under triaxial
loading and its application. Int. J. Mech. Sci., 42, pp. 617633, 2000.
[7] Huh, H., Kim, S. B., Song, J. H. & Lim, J. H., Dynamic tensile
characteristics of TRIPtype and DPtype steel sheets for an autobody. Int.
J. Mech. Sci., 50, pp. 918931, 2008.
[8] Huh, H., Lim, J. H. & Park, S. H., High speed tensile test of steel sheets for
the stressstrain curve at the intermediate strain rate, Int. J. Automotive
Technol., 10(2), pp. 195204, 2009.
[9] Huh, H., Yoon, J. H., Park, C. G., Kang, J. S., Huh, M. Y. & Kang, H. G,
Correlation of microscopic structures to the strain rate hardening of SPCC
steel. Int. J. Mech. Sci., 52, pp. 745753, 2010.

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Materials Characterisation V

227

Definition of averaged elastic-plastic


characteristics of sandwich panel structures
I. I. Zakirov, V. N. Paimushin & I. M. Zakirov
A. N. Tupolev State Technical University, Kazan, Russia

Abstract
Analytic formulas for averaged elastic and strength characteristics of folded
structures determination are identified. They are based on the introduction of a
hypothesis about momentless action of its elements (web covers) in a charge
operation and on phased deletion from action ex-post buckling. Dimensionless
coefficients contained in the structural formulas, which appear on the solution
process of formulated problems, are to be determined from experimental
evidence on tension, compression and pure shear in two-planes. In a tensioncompression process the folded structures should be considered heterogeneous
material with averaged plasto-elastic behaviors, which has relations between
averaged voltages and averaged appropriate deformations and has a deformations
stepwise change area (conditional plastic flow).
Keywords: folded structures, cell of cyclicity, averaged elastic and strength
characteristics, modulus of elasticity, deformation curve, structural formulas,
theoretical and experimental method.

Introduction

In many cases, the use of composite materials is the most efficient in


constructions (three-layer or multilayer) with cores, which have good mechanical
strength, rigidity, vibration, sound and heat insulation characteristics. These
characteristics of cores of some structures have been well studied today. A large
number of publications, a detailed analysis of which is contained, in particular, in
a review article [1] are devoted to their research.
Most often in three-layer and multilayer structures, the cores have a
honeycomb ([2, 10] etc.) structure. In the calculations of such structures the real
cores are usually replaced by some homogeneous continuum, which averaged
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doi:10.2495/MC110201

228 Materials Characterisation V


mechanical and thermal characteristics are determined by the principle of
equivalence of real and replacing core [35]. At such replacement of real
honeycomb with orthotropic continuum for the strength calculations averaged
elastic module in the tangential directions and the shear modulus in the
tangential plane are set equal to zero, and the elastic modulus in the transverse
direction and shear module in the transverse plane is determined by theoretical or
experimental methods [8, 10]. Formulas for their determination are given, in
particular, in references [3, 4] that, as a first approximation of formulas, have
been obtained by the energy method [3], or the method of displacements and
forces [6]. Along with these, there are other theoretical methods for determining
the averaged elastic characteristics of periodic structures based, in particular, on
the method of averaging the solution of problems by Bakhvalov and Ponasenko
[7].
In recent years, ways of production of the folded structures from flat sheets
cores [11, 12] develop very intensively. Such cores compared with honeycomb
cores have a number of fundamental differences and advantages. In this paper we
consider one of these folded structures. We develop relevant theoretical and
experimental method to determine the homogenized elastic and strength
characteristics of which.
1.1 Formulation of the problem
Consider folded structure with a quadriradiare core [11], formed from a flat sheet
blank with thickness t by means of its gradual transformation into a state of

relief, as shown in Figure 1a. We assume that, in general, l1 l2 , 1 2 and


all four sloping walls 1,1, 2, 2 of the periodicity cells isolated from the core
are a parallelogram, symmetrically placed relative to the plane
the middle planes

x01 z . Therefore,

k of each of them reasonable classified as a local oblique

xk 0k yk and xk 0k yk , in which (Fig. 1a) xk xk and the


radius vectors of the points k given by a representation
coordinate system

r xk e1 yk e2 , r
k

In them unit vectors

k
k
xk e1 yk e2

(1.1)

ei k , ei k satisfies the equations

ei ei 1, ei ei
k

1, e1 e2 e1 e2 cos k
k

(1.2)

which according to Fig. 1a and 1b with unit vectors i , j , k of orthogonal


Cartesian coordinate system related with dependencies

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Materials Characterisation V

229

ie1 k ie1 k cos k , ie2 k ie2 k sin

je2 k cos , je2 k cos , je1 k je1 k 0

ke11 ke11 sin 1 , ke1 2 ke1 2 sin 2

(1.3)

ke2 k ke2 k 0

()

(b)
Figure 1.
Parameterizations (1.1) correspond to the basis vectors (for the elements

1 and 2 compiled following relations must be marked with strokes)


r1 r
k

xk e1 , r2 r
k

yk e2

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(1.4)

230 Materials Characterisation V


co- and contravariant components of metric tensor

aii ri ri 1, a12 a21
r1 r2 cos k
k

aiik

(1.5)

k
12

aii
cos
1
a
, a12k a21k

2 k
2
a k sin k
a k
sin k

k k

k k

where a k a11 a22 a12 a12 1 cos

(1.6)

k sin 2 k .

For the displacement vectors of core walls we accept following


representations
U k u k e1k v k e2k w k m k z k k e1k k e2k

t 2 z k t 2

(1.7)

eik are the reciprocal basis vectors satisfying the conditions

where

eik e j ij ( ii 1, ij 0 where i j ), aijk eik ejk , m k are the unit


k

vectors

normal

to

the

plane

k ,

satisfying

the

equations

ei m 0, m m 1 .
k

According to the Kirchhoff-Love model, with an average bending for the


functions

and

will take place following dependences.

k w,xk , k w,yk
where

, x

xk . By using these relations for the covariant

components of the tangential deformations are established following relations.

ij ij k z k ijk
zk

(1.8)

where

1
2
k
k
k
k
u, y v,x w,x w,y

1
2

11 k u,xk w,xk w,xk , 22 k v,yk w,yk w,yk


k

212

k
k
11
w,xxk , 22k w,yyk , 12
w,xyk

(1.9)

(1.10)

Under the assumption of linear elastic behavior of core material when it is


loading the contravariant components of the tension tensors in the walls
with deformation tensor components

ij
zk

ijk

are related by the elasticity

correlation of the following form


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Materials Characterisation V

ijk

E
z
Eijml
k
k ml
2
1 v

231

(1.11)

where E , v are the Youngs modulus of elasticity and Poisson's ratio of wall
ijml

material, and E k is the tetravalent tensor of the elastic characteristics,


components of which for an isotropic material in plane stress state are defined by
correlations

Eijml
vaijk amlk
k

1 v im jl
a k a k ailk ajm
k
2

(1.12)

Substitution of formulas (1.6) to the correlations (1.12) leads to the formulas


v sin 2 k cos 2 k
1
E1111
E2222

, E1122
E2211

,
k
k
k
k
2
sin k
sin 4 k

E1112
E1121
E1211
E2111
E1222
E2122
E2212

k
k
k
k
k
k
k
E2221

cos k
,
sin 4 k

E1212
E2121
E1221
E2112

k
k
k
k

1 cos 2 k v sin 2 k
2sin 4 k

(1.13)

We assume that under the loading of the core in the sandwich and multilayer
structural elements in its walls because of their small thickness realized the flat
and membranaceous stress-strain state. In this case, accumulated in them
potential energy of deformation is permissible to calculate by the following
formulas
l d
1k
k
(1.14)
sin k dxk dyk
k t 11k 11 k 2 12k 12 k 22k 22
200

where d k

ak dxk dyk sin k dxk dyk is the area of infinitely small


element of the middle plane of k -th core wall, and the components of the
deformation

ij k are defined by correlations (1.9). These correlations are written

in linear approximation by dropping the nonlinear terms. After the transition


from a flat membrane state in the perturbed moment state possible due to a loss
of stability of the flat form of equilibrium. To study the perturbed neutral
equilibrium state we will use the variational equation of the Ritz method,
compiled on the basis of relations (1.8)(1.11).
In the space V of a selected cell of periodicity, referred to orthogonal
Cartesian coordinates x, y and z , averaged elastic properties of the core should
be considered orthotropic. The elastic modulus of the first kind Ez in the
direction z and the modules of the transverse shifts Gxz , G yz in the planes xz
and

yz must be determined within the bounds of the model of a transversely


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232 Materials Characterisation V


soft core. If the displacement vector of any point M V provide an expansion
U ui vj wk and in cross-sections x const , y const , z const
introduce the averaged voltage

xz , yz , z

the accumulated in the volume

strain energy will be determined by the expression

1
xz xz yz yz z z dV
2
V

where for calculation the transverse shear strain

xz , yz

(1.15)

and axial strain

of

the homogenized medium in the linear approximation we have the kinematic


relations

xz

u w
v w
w
, yz
, z

z x
z y
z

(1.16)

Using of the principle of equivalence of real and replacing conditional core with
average elastic and strength characteristics requires to preparation of the
equality.

(1.17)

which will be used for further calculations.

2 Critical values of the tensions formed in the walls of the


core when it is loading
Assume that in walls of the core in terms of loading formed homogeneous in
their middle plane tensions

11k , 22k

and

12k .

To produce the approximate structural formulas for using of theoretical and


experimental
method
[8],
the
edges
of
the
walls
xk 0, xk lk , yk 0, yk d will be assumed simply supported.
Whether for these or other types of loading in the walls of the core forms only
compressive tensions

11k

and

22k ,

and

12k 0 ,

when taken under

consideration pinning the edges of the walls to construct the solution of the
stability function w

can be represented as

k
w k Amn
sin

m xk
m yk
sin
lk
d

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(2.1)

Materials Characterisation V

233

where m 1, 2,..., n 1, 2,... are the wave numbers. Then with the
introduction of the dimensionless parameters

lk
,
d

11k it is possible to receive the formula

For definition of critical value

Kx

11
k

k 22k 11k .

Dk
2E t
k
K x Dk , Dk

sin 4 k
12 1 v 2 lk

(2.2)

where
k

Kx

k2 n 2 4m 2 n 2 k2 cos 2 k
2

m k n
2

2
k

, Dk

to construct the solution of the stability function w

represented as

w k W k sin
In a case

(2.3)

11k 0 , 12k 0

In general, the subcritical tension state, when

22k 0

Dk
sin 4 k

11k 22k 0 ,

critical tension

12k

k 5.34 4

yk
lk

sin

and

can be

yk kk xk

(2.4)

using the (2.4) for determination the minimum

it possible to receive an approximate formula

lk2
2
Dk 1 cos k
d2

2
1 cos k
1 cos 2 k

(2.5)

3 Determination of elastic and strength characteristics


Displacement vector in a space V of core we can represent in the form

z
(3.1)
u0 i v0 j w0 k , 0 z h
h
where u0 const , v0 const and w0 const moving the points of the
z h,
with
a
net
in-plane
shear
boundary
plane

x01 z u0 0, v0 0, w0 0 , y 01 z u0 0, v0 0, w0 0

and

tension-

k 1, 2,1, 2

(3.2)

compression in the direction of the axis 01 z . We denote

U 0 k u0 k e1k v0 k e2k w0 k m k

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234 Materials Characterisation V


displacement vectors of faces x1 x1 l1 and x2 x2 0 walls of the filler,
and for the displacements U

of the points M k k we take the

approximations

x1 1 1 x1 1 2 x2 2
U 0 , U U 0 , U 1 U 0
l1
l1
l2
x 2
1 2 U 0
l2

1
U

(3.3)

The condition of equivalence of the real and the conventional core requires the
satisfaction of the equality
k
k
k
k
k
(3.4)
u0 i v0 j w0 k U 0 u0 e1k v0 e 2k w0 m k 1, 2,1, 2

Scalar multiplication of both sides by vectors ei

and using (1.2) (1.3), we

arrive to the dependencies

u0 u0 cos 1 w0 sin 1 , v0 u0 sin v0 cos


1

u01 u0 cos 1 w0 sin 1 , v01 u0 sin v0 cos

u0 u0 cos 2 w0 sin 2 , v0 u0 sin v0 cos


2

(3.5)

u0 u0 cos 2 w0 sin 2 , v0 u0 sin v0 cos


2

In component form the vector equalities (3.4) lead to the approximating


functions

u 1

x1 1 1 x1 1 1 x1 1 1 x1 1
u0 , v v0 , u u0 , v v0
l1
l1
l1
l1

x 2 2 x 2
2
u 1 2 u0 , v 1 2 v0
l2
l2

(3.6)

x
x

u 2 1 2 u0 2 , v 2 1 2 v0 2
l2
l2
By the substitution into the linear kinematic relations

11 k u,xk , 22 k v,yk , 212 k u,yk v,xk

(3.7)

compute the components of deformation in the walls of the core in the membrane
approximation.
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Materials Characterisation V

235

Compiled on the basis of the relations, we consider the case of the periodicity
cell of core by tension and compression along the axis z w0 0, uo v0 0
in the case of loading we can get formulas:

11 k 11 k sin 2 k

w0 k
k
k
k
, 22 22
12 12 0
h

E
E sin 2 k w0
1111 k

E 11
1 v2 k
1 v 2 sin 4 k h
E
E2211
22k
11 k v sin 2 k cos 2 k 11k
k
2
1 v
2 E 1211 k
E 11 cos k 11k
12k
1 v2 k

(3.8)

11
k

(3.9)

From which follows that in the condition of tensile fracture of core ( w0 0 ) is


possible because of the destruction of the adhesive layer connecting the core with
a bearing layer, and while compression ( w0 0 ) due to loss of stability of the
walls in her bilateral compression and shear.
When we approximating the displacements of the averaged core (3.1), it
formed the strains and stresses

w0
u
v
w
, xz 0 , yz 0 , 33 Ez 0
h
h
h
h
(3.10)
u0 23
v0
13
Gxz , G yz
h
h
where the homogenized elastic modules Ez , Gxz and G yz must be determined.

By using the relations (3.10) in accordance with expression (1.15) for calculation
we arrive at the formulas in the case u0 v0 0

hd ctg1 ctg 2 sin 33 w0

(3.11)

d ctg1 ctg 2 sin Ez w

(3.12)

2
0

and by using relations (3.8) and (3.9), in accordance with (1.14) for calculation
k we arrive to the formulas

sin k sin k
w0 k 1, 2,1, 2
2

(3.13)

sin 3 k w02
E
td
k 1, 2,1, 2
1 v 2 2sin 3 k h

(3.14)

11k td

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236 Materials Characterisation V


By substituting relations (3.12) , (3.14) from equation (1.17) we can obtain a
formula to determine Ez

Ez

2
sin 3 k
E
t

1 v 2 h ctg1 ctg 2 k 1 sin 3 k

(3.15)

and using (3.13) from (1.17) we can obtain the following dependence

33

2
t
11k sin k sin k

h sin ctg1 ctg 2 k 1

In the case of the maximum tensile stresses

11k , 22k , 12k

(3.16)

are largest in the

k sin 2 k sin 4 k .The process of

destruction in it begins when certain tensile strength is reached. As in real


cores, angles k and k do not have significant difference, it is possible to
11
11
assume that when the strength reaches 1 or 2 the simultaneous failure of all

wall, in which the maximum value is

four walls of the core begins. Under these assumptions to determine the limit

33

at which the core is destroyed we can create equality

33

2
t
sin k sink

h sin ctg1 ctg 2 k 1

(3.17)

33
From it by the experimentally determined value determined the quantity

.
When compressing of the core begins its destruction due to the destruction of
the buckling of the wall, which formed the voltage

k v sin 2 k cos 2 k

11k

and cos k

at a given dimensions

12k 11k

reaches a critical value

11
k

Kx

t
2 E sin 2 k t
k
Kx
(3.18)
12 1 v 2 sin 4 k lk
12 1 v 2 sin 4 k h

2E

Assuming further that for the real core loss of stability of a wall immediately
causes a loss of stability of a second wall, we form the equation

11k 11k ,

from which to determine the lateral deformation at the moment of loss of


stability [9] by using relations (3.9) and (3.18) follows the formula

2 t
w0

K
x


12 h
h

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(3.19)

Materials Characterisation V

where K x K x

237

K x . However

2E
t
K x

2
12 1 v sin ctg1 ctg 2 h
33

For given parameters E , , t h , k and


determined value of critical stress

k of

33 of

sin 3 k

sin
k 1

(3.20)

the core the experimentally

the derived formula (3.20) is

determined by a dimensionless coefficient K x .


Elastic and strength characteristics of the core in a shift in planes XoZ YoZ
are defined by analogy with the stated above.

Conclusions

Theoretical and the experimental methods presented in this article allow to


define the averaged elastic and strength characteristics of sandwich folded fillers
on the basis of use of analytical expressions for definition of the critical tensions
formed in walls of a filler while loading.

References
[1]

[2]
[3]
[4]
[5]

[6]
[7]
[8]

[9]

Noor A. K., Burton W.S., Bert Ch. W., Computational models for
sandwich panels and shells. Applied Mechanics Reviews, 1996, V. 49,
3, p. 155-199.
Bersudsky V.E., Krisin V.N., Forest S., Manufacturing technology of
cellular aircraft structures. - Moscow: Mashinostroenie, 1975. 216s.
Aleksandrov A.Y., Bryukker L.E., Kurshin L.M., The calculation of
sandwich panels / M. Oborongiz, 1960. 272s.
Panin V.F., Gladkov Yu.A., Constructions with cores. Directory.
Moscow: Mashinostroenie. 1991. 272s.
Kryutchenko V.E., Analysis of optimum insulation properties of
sandwich plates with honeycomb core. /Mechanics of Composite
Materials. - 1993, T.29.- 6.- S.835-839.
Relsey S., Gellatly H. and Clark B., The shear modulus of foil
honeycomb cores. Aircraft Engineering. 1958. V.30. 356. P.294-302.
Bakhvalov N.S., Ponasenko G.P., Averaging of the processes in periodic
media.- Moscow: Nauka, 1984. 352 c.
Sachenkov A.V., Theoretical and experimental method for studying the
stability of plates and shells. Investigations on the theory of plates and
shells. Kazan: Izdatel'stvo Kazan. State. Univ. - 1970, Vol. 6.7.- S. 391433.
Volmir AS Stability of elastic systems. M.: Gos. out of Sci. literature.
1963. 880 sec.

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238 Materials Characterisation V


[10]

[11]

[12]

Akishev N.I., Zakirov I.I., Paimushin V.N., Shishov M.A., Theoreticalexperimental method for determining the averaged elastic and strength
characteristics of honeycomb of sandwich structures. Mechanics of
Composite Materials. - 2011 (in press).
Zakirov I.M., Alekseev, K.A., Akishev N.I. Kayumov R.A., NikitinA.V.,
Zakirov I.I., Manufacturing of sandwich panels with folded core of
polymer paper Kazan: Publishing house Fan 2009
Zakirov I.M., Alekseev K.A., Determining of the parameters of the four
radial helical folded structure / IVUZ Aviatcionnaya technika 2005

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Materials Characterisation V

239

Hot deformation and mechanical properties


of P/M Al special
M. Tercelj, P. Cvahte, I. Perus & G. Kugler
Faculty of Natural Science and Engineering, University of Ljubljana,
Slovenia

Abstract
Almost pure aluminum composite, P/M Al-special, with an average grain
diameter of 1m with oxides on the grain surface was produced by a powder
metallurgy route. Billets were extruded on an indirect press at various
temperatures and ram-speeds. Specimens made from an extruded profile were
additionally annealed at 300C at various times. Hot workability of these various
initial states was studied by hot compression tests in the strain rate range 0.01
10 s-1, the temperature range 300580C up to a strain of 0.9. Additionally tensile
tests were carried out to determine the mechanical properties on specimens
previously annealed at 300C. The oxide surface prevents grains coarsening
during hot deformation and consequently excellent mechanical properties of the
specimens annealed at a temperature of 300C were obtained.
Keywords: P/M 1080 Al composite, hot extrusion, annealing, hot compression,
mechanical properties.

1 Introduction
Demands for weight reduction of parts applied in cars and aircrafts has lead to
the replacement of conventional materials with lighter and stronger materials.
Aluminum alloys have a great potential for this application but their weaknesses
are too low strength and stiffness. On the other hand production of parts from
metal-matrix composites which is based on the reduction of grain size is very
promising due to their unique mechanical properties in comparison with coarsegrained materials [16].
Powder (P/M) and ingot metallurgy which include particle reinforcement
mixing with solid or molten metal assure production of composites with
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doi:10.2495/MC110211

240 Materials Characterisation V


improved mechanical, physical and thermal properties. Hard particles like
ceramic, carbides, oxides or nitrides are usually finely dispersed in Al alloy
matrix. For P/M the size of the powder can be in the range between several tens
of nm to hundred m, while the sizes of reinforcing particles are accordingly
lower. Thus with P/M a finer microstructure with a uniform distribution of
micro-constituents can be obtained which leads to mechanical properties, i.e.
stiffness, strength and wear resistance, etc. which are usually better than those
obtained for materials produced by casting procedures [416, 2325].
Mechanical parts made from aluminum-matrix composites (AMCs) are
usually produced by conventional hot deformation processes such as rolling,
extrusion, forging, etc. Thus understanding of the behaviour of the material
during hot working is essential for optimization of the intrinsic workability,
control of evolution of microstructure, and for optimization of the production
process. Hot workability studies revealed that AMCs are usually more sensitive
to strain rate and temperature in comparison to conventional aluminum alloys.
Namely, grain boundary sliding that takes place at higher temperatures and/or
lower strain rates can lead to the formation of wedge-shaped cracks at grain
boundaries. Additionally, the presence of hard particles in the softer matrix can
result in plastic flow localization at the particle-matrix interface. Furthermore
during hot extrusion of AMCs prior grain boundaries are usually removed due to
diffusion, recovery, etc. that results in reduced mechanical properties. Increasing
of grains during processing can be partly prevented by fine dispersion of ceramic
particles. For such ultra-fine grained materials with a mean grain size of 1m and
below, different deformation mechanisms are operative than for coarser-grained
materials. Namely in very small grains the accumulation of dislocations become
difficult that leads to decreased ductility of fine grained AMCs, also at room
temperature [523]. While for conventionally (by casting) produced AMCs the
hot deformability has been studied in several publications [1422, 2630], hot
deformation of P/M AMCs has found considerably less attention [5, 2325, 31
34]. Only a few studies on P/M AMC using pure aluminum as a matrix exist.
These studies report that pure Al may benefit more from brittle reinforcement
particulates than Al-alloys [5, 35, 36].
The aim of this work is to produce a new fine grained P/M Al-special matrix
composite on the base of almost pure Al with an oxide surface on grains aiming
to prevent excessive grain coarsening during hot extrusion and followed by a hot
deformation process as well as assessment of appropriate hot working
parameters. Furthermore the mechanical properties were determined after the
extrusion process as well as after various annealing times.

2 Experimental procedures
2.1 Material and characterization of microstructure
A JSM-5610 energy dispersive spectrometer from iXRF Systems Inc. with a
digital processor 500 for chemical analysis of P/M Al-special was used along

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Materials Characterisation V

241

with a transmission electron microscopic (TEM, JEOL-2021) for microstructural


characterization.
2.2 Processing of initial P/M Al-special
The P/M Al-special was produced according to the routes given in fig. 1. Powder
was produced by Vacuum Powder Metallurgy, with a special grain powder
process. Adding of various additives and lubricants is aimed to accelerate the
diffusion processes in bulk material that represents the next step of preparation
of powder mixture. After Rubber Isostatic Pressing (RIP) or Cold Isostatic
Pressing (CIP) with application of a typical pressure of 100 MPa, the achieved
density was 85%. Then follows the thermal preparation of billet (dehumidifying
cycle) and machining of the billet to dimensions of 274 mm. The hot extrusion
was carried out on an industrial 35 MN indirect press. After extrusion the
achieved density was 95% while following hot compression this value was 100%
(see fig. 1).

Figure 1:

Processing routes for P/M 1080Al composite.

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242 Materials Characterisation V


2.3 Hot extrusion
Indirect hot extrusion at various billets temperature and extrusion speeds was
employed to convert the processed powder to bulk material.
2.3.1 Extrusion of P/M Al-special on 35 MN indirect press
Initial powder billets of dimensions 274 x 1500 mm were hot extruded to a flat
bar. Die dimension was 91.3 x 50.8 mm and extrusion ratio was 13.3. Maximum
press pressure in the main cylinder is 250 x 105 Pa, which corresponds to a force
of 35 MN. Billets 2 and 3 are heated in a die furnace (indirect) to 340C and
320C, respectively, while billet 1 was heated in an induction furnace to 420C.
Ram speeds were in the range 3.898.87 mm/s. Other data applied at extrusion
of P/M Al-special on the 35 MN indirect press are collected in Table 1.
Table 1:

Technological data - Flat bar 90x50 (0.9) mm, alloy P/M


Al-special, indirect extrusion.

Technological data; die opening: billet dimension: 274 mm x 1500 mm,


91.3 mm x 50.8 mm, container dimension 280 mm, extrusion ratio: 13.3
Billet material

P/M Al-special
1st billet

2nd billet

3rd billet

Billet length (mm)

500

500

500

Container temperature (C)

360

360

360

Billet temperature (C)

418

340

320

Ram speed (mm/s)

8.87

6.2

3.89

Puller speed - bar speed (m/min)

7.06

4.94

3.10

Press rest (mm)

50

50

50

2.4 Annealing
In order to investigate the influence of elevated temperature on recrystallization
resistance, annealing tests were carried out at temperatures of 300C and
employed at different times, i.e. 1, 5, 9 and 20 hours.
2.5 Hot compression and tensile tests
Hot workability was studied by hot compression tests. Cylindrical specimens of
Rastegew type with dimensions =10 mm x 15 mm were cut from the extruded
profile (3rd billet) so in non-annealed states as well as in annealed states, i.e.
previously annealed at 300C for 1, 5, 9 and 20 hours, respectively. Hot
compression of extruded material was carried out on a computer controlled
servo-hydraulic machine, Gleeble 1500D, in the temperature range 300C to
570C, at five different strain rates (0.01, 0.1, 1 and 5 or 10 s-1) up to a strain of
0.9, while for the annealed material from a production point of view only at a
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Materials Characterisation V

243

strain rate range 0.15 s-1. The heating rate was 1C/s and the soaking time at
compression temperature was 1 minute. For reduction of friction between the
cylindrical specimen and the tool, and in order to avoid their mutual welding,
graphite lubricant and tantalum follies were used. After deformation the
specimens were water quenched. The conditions for hot compression testing are
given in Table 2.
For determination of tensile strength and elongation at room temperature
tensile tests were carried out on a Zwick Z400 according to standards (SIST EN
10002-1:2002, 5th edition, June 2002). Tensile specimens was cut out from the
centre of the extruded bar, the working length of the tensile specimens was 50
mm with a diameter of =10 mm. Tensile tests were also carried out also on a
AA 1050.
Table 2:
State of material
Extruded
Annealed

Hot compression test conditions.


Hot compression tests
Temperature, C
Strain rate, s-1
300570
0.0110
300570
0.0110

Strain range
0-0.9
0-0.9

3 Results and discussion


3.1 Composition and microstructures of initial materials
The bulk materials consist of 99.44 wt% Al, 0.034 wt% Si, 0.159 wt% Fe, while
oxygen (0.363 wt%) is contained on the grain surface. Initial microstructures of
loose and compacted powder P/M Al-special are given in figs. 2a-b, respectively.
It is visible that the average diameter of powder grains is around 1m and that
the surface layer of grains consists of aluminum oxide (Al2O3) to prevent
possible diffusion, recovery processes, i.e. to prevent grain growth during hot
deformation.

Figure 2:

Initial microstructure of P/M Al-special: loose powder (a) and


compacted powder with visible oxides on grain surface (b), TEM.

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244 Materials Characterisation V


3.2 Indirect hot extrusion of P/M Al-special
The time courses of oil pressure in the cylinder for various billet temperatures as
well as for ram speeds are shown on fig. 3. The lowest pressure of 215 x 105 Pa
(177 bars) was obtained as expected at the highest billet temperature (418C) and
highest ram speed (8.87 mm/s). On the other hand at the very beginning of the
extrusion of the third billet almost the maximal oil pressure was achieved while
the highest pressure at the lowest billet temperature (320C) and lowest ram
speed (3.89 mm/s). The highest oil pressure 215 x 105 Pa (215 bars) was
achieved at lowest billet temperature, i.e. at 320C.

Figure 3:

Time course of oil pressure in the cylinder during hot extrusion on


the indirect press at various ram speed for P/M Al-special, 35 MN
indirect press.

3.3 Hot workability of extruded and annealed P/M Al-special


Compression tests were carried out for extruded as well as for annealed states.
On fig. 4a the typical microstructure of the extruded profile and on fig. 4b the
microstructure of deformed samples which have been previously annealed for 20
hours at a temperature of 300C are presented. It is visible that the oxide surface
on P/M grains is partly damaged but the average diameter of grains is only
slightly increased in comparison to the initial state (ca 1m, see fig. 2b). The
figure clearly reveals that the oxide surface prevents grain growth.
Obtained flow curves for extruded P/M Al-special are shown on fig. 5. From
deformed specimens and the shape of flow curves it can be seen that carrying out
the hot deformation at lower strain rates (0.010.1 s-1) is not appropriate since on
specimens cracks occurred; this results in rapid fall of flow curves in the strain
range 0.40.5 as can be seen for the strain rate of 0.1 s-1 on fig. 5, left. The
behaviour can be ascribed to the usual problem of low-strain rate/hightemperature plasticity of P/M Al-alloys described in several studies such as in
[3741].

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Materials Characterisation V

Figure 4:

245

Microstructures of extruded P/M Al-special: extruded (a), and


forged and annealed (b).

At higher strain rates the flow curves after achieving the maximal value at the
very beginning of hot compression, i.e. in the strain range up to 0.03, the values
of flow stress begin slightly to fall approaching a steady state (see fig. 5, right).
Moreover, at higher strain rates (110 s-1) the cracks did not occur that is
expressed also by the shape of flow curves.

Figure 5:

Flow curves of P/M Al-special (extruded state) at various


temperatures and stain rates.

As mentioned the hot compression tests were carried out also for samples
annealed at various times. The shapes of flow curves obtained after various
annealing times and for a strain rate of 5 s-1 are similar to those obtained for the
extruded state but in general their values decrease up to an annealing time of 5
hours (see fig. 6). It is visible that values of flow curves are considerably lower
(about 15%) for annealed states in comparison to non-annealed states. During the
extrusion a small percentage of the oxide layer on the grains are torn. This may
allow re-arrangement of some grains with orientation changes. During annealing
of extruded material the process of part polygonization starts. After one hour at
300C material became stable since grain growth was blocked by oxides.

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246 Materials Characterisation V

Figure 6:

Comparison of flow curves between extruded and at various


annealing times for P/M Al-special; strain rate 5 s-1, annealing
temperature 300C.

3.4 Obtained mechanical properties


The general presentation of the obtained mechanical properties, i.e. tensile
strength and elongation, of P/M Al-special (indirect extrusion) is shown in fig. 7.
The values of tensile strength of around 209 MPa and 205 MPa for the nonannealed and 20 hour annealed state were obtained, respectively. Furthermore,
values for elongation for the non-annealed state were around 24% while for the
20 hour annealed samples these values slightly decreased and were around 23%.

Figure 7:

Tension curves vs. for P/M Al-special at various states and


times of annealing.

For comparison for AA 1050 the values for strength were around 80 MPa and
for elongation were around 38%. Thus around 2.6 times higher values for tensile
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Materials Characterisation V

247

strength and 1.6 times lower values for elongation for P/M Al-special in
comparison to AA 1050 were obtained.
From the obtained results for P/M Al-special it can be derived that this
material can be applied also at elevated temperatures. It is also worth mentioning
that in our case grains consist only of almost pure Al and without particles in the
matrix. Thus the achieved mechanical properties are also on a relative high level.

4 Conclusions
New P/M Al-special composite made from almost pure Al with an average
diameter of 1m and with oxides on the grain surface was developed. The
achieved density after cold isostatic pressing was 84%, after hot extrusion 96%
and 100% after hot compression. The P/M Al-special material exhibited a good
combination of strength and elongation properties also at samples previously
exposed to elevated temperature.
The produced P/M Al-special has a great potential to substitute the classical
aluminum alloys and steels in the field of an elevated temperature working
environment. The obtained values for tensile strength for P/M Al-special alloy
are up to 2.6 times higher and for elongation around 1.6 times lower in
comparison to values obtained for AA 1050 aluminum alloy produced by
classical technology. The tensile strength of samples taken from extruded billet
with an extrusion ratio of 13.3 reaches a value of about 209 MPa while achieved
elongation was around 24%. The material exhibits good resistance against
increasing of grain size at elevated temperature. After 20 hours of annealing the
tensile strength slightly decreased and reached the value of 204 MPa. On the
other hand the value for elongation remains almost at the same level, i.e. 23%.
Extruded material exhibited low hot deformability at strain rates of 0.1 s-1 and
lower, while at higher strain rates the compressed samples were crack free.

Acknowledgements
The authors gratefully acknowledge Martin Balogand and Karol Idinsk from
Slovak Academy Of Sciences, Institute of Materials and Machine, Mechanics
Raianska 75, 831 02 Bratislava 3, for their contribution towards analyzing the
powder.

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Bardi, F., Cabibbo, M., Evangelista, E., Spigarelli, S., Vukcevic, M., An
analysis of hot deformation of an AlCuMg alloy produced by powder
metallurgy, Materials Science and Engineering: A, 339(1-2), pp. 43-52,
2003.
Badini, C., La Vecchia, G.M., Fino, P., Valente, T., Forging of 2124/SiCp
composite: preliminary studies of the effects on microstructure and
strength, Journal of Materials Processing Technology, 116(2-3), pp. 289297, 2001.
Luo, H., Shaw, L., Zhang, L.C., Miracle, D., On tension/compression
asymmetry of an extruded nanocrystalline AlFeCrTi alloy, Materials
Science and Engineering: A, 409(1-2), pp. 249-256, 2005.
Cerri, E., Spigarelli, S., Evangelista, E., Cavaliere, P., Hot deformation and
processing maps of a particulate-reinforced 6061+20% Al2O3 composite,
Materials Science and Engineering: A, 324(1-2), pp. 157-161, 2002.
Zhang, H., Ramesh, K.T. Chin, E.S.C., High strain rate response of
aluminum 6092/B4C composites, Materials Science and Engineering: A,
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[30] Ccen, ., nel, K., Ductility and strength of extruded SiCp/aluminiumalloy composites, Composites Science and Technology, 62(2), pp. 275-282,
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[31] Malas, J.C., Venugopal, S., Seshacharyulu, T., Effect of microstructural
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[32] Staehler, J.M., Predebon, W.W., Pletka, B.J., Subhash, G.,
Micromechanisms of deformation in high-purity hot-pressed alumina,
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[33] Evangelista, E., Forcellese, A., Gabrielli, F., Mengucci, P., in: T.G.
Langdon, H.D. Merchant, J.G. Morris, M.A. Zaidi (Eds.), Hot Deformation
of Aluminium Alloys, The Minerals, Metals and Material Society,
Warrendale, PA, pp. 121-130, 1991.
[34] Cerri, E., Evangelista, E., Forcellese, A., Fiorini, P., Stobrawa, J., Strength
and ductility of powder metallury aluminum alloys under hot working
conditions, in: H. Oikawa, et al. (Ed.), Strength of Metals and Alloys, The
Japan Institute of Metals, Tokyo, pp. 807-810, 1994.
[35] Lai S.W., Chung, D.L., Superior high temperature resistance of aluminum
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[36] Mazen, A.A., Ahmed, A.Y., Mechanical behaviour of AlAl2O3 MMC
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of 6061 Al, Acta Metall. Mater.,42, pp. 667-678, 1994.
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Materials Characterisation V

251

Coarsening kinetics of the bimodal


distribution in DS GTD111TM superalloy
V. S. K. G. Kelekanjeri1, S. K. Sondhi2, T. Vishwanath1,
F. Mastromatteo3 & B. Dasan2
1

GE Global Research Center, Materials Characterization Laboratory,


Bangalore, India
2
GE Global Research Center, Materials Research Laboratory,
Bangalore, India
3
GE Oil & Gas, Nuovo Pignone, Materials & Processing Engineering,
Florence, Italy

Abstract
Coarsening of precipitates in nickel-base superalloys is one of the mechanisms
by which creep damage occurs in these alloys. This is brought about by a
concomitant increase in the interparticle spacing, which results in faster
dislocation movement and therefore, faster creep strain accumulation. Therefore,
it is vital to accurately quantify the coarsening kinetics, which is essential for
creep prediction via microstructure-based continuum damage mechanics models.
In the present article, we report on coarsening studies of bimodally distributed
precipitates in DS GTD111TM (Trademark of the General Electric Company).
The baseline microstructure of GTD111TM consisted of a cuboidal secondary
population and a much finer, spherical tertiary population with respective
mean radii of 266 and 34nm. Long-term aging experiments were conducted on
baseline samples at temperatures of T1<T2<T3<T4 in the range of 800 to
1000C. At T1, there was no clear trend in coarsening of the secondary , likely
due to interference effects from the tertiary distribution. Therefore, secondary
coarsening was studied using data at higher temperatures where the distribution
was clearly unimodal. The kinetics was extracted assuming the cubic rate law to
be valid under conditions of volume diffusion controlled coarsening.
Subsequently, the secondary kinetics was applied to predict coarsening of the
tertiary distribution at T1 by incorporating a correction factor for volume fraction
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doi:10.2495/MC110221

252 Materials Characterisation V


enhancement of coarsening. Separately, the expected rate of tertiary
coarsening was computed by compensating for volume fraction loss of tertiary
between successive aging steps consumed during secondary coarsening. The
coarsening rate constants from these two approaches were comparable. In
summary, the present work is a treatment of bimodal coarsening kinetics in
GTD111TM where coarsening of the individual distributions are captured using a
single consistent LSW rate equation.
Keywords: nickel-base superalloy, GTD111TM, precipitate, - microstructure,
bimodal distribution, coarsening, ostwald ripening, kinetics, creep, continuum
damage mechanics.

1 Introduction
GTD111TM is a directionally solidified nickel-base superalloy which is used in
hot gas-path sections of gas turbines at temperatures of 750 to 800C [1]. The
presence of a bimodal distribution of the (Ni3(Al,Ti)) precipitate phase
contributes to superior high temperature strength [2] of the alloy. However, upon
prolonged thermal exposure, the distribution undergoes coarsening [3],
resulting in an increase in the average interparticle spacing. This leads to easier
movement of dislocations in the alloy and consequently, lower creep resistance
[4]. In this context, coarsening as a damage mechanism warrants a detailed
study so that an understanding of the kinetics of microstructure degradation may
subsequently be used to develop continuum damage mechanics models.
Coarsening studies in multimodal precipitate systems has been reported in
literature in both blade alloys such as GTD111 [5] and IN738 [6] and disc alloys
such as Nimonic 115 [7] and Waspaloy [8]. Sharghi Moshatghin and Asgari [9]
studied coarsening of bimodal distribution in IN738LC in terms of a
compound size parameter that incorporates both primary and secondary
dimensions. They found that the kinetics analyzed using this size parameter
followed the cubic rate law in the range of 850 to 900C. Stevens and Flewitt [6]
reported volume diffusion controlled coarsening kinetics for both secondary and
tertiary in IN738 in the temperature range of 750 to 850C. Coakley et al. [7]
implemented the numerical mean-field model based on the LSW theory,
originally developed by Chen and Voorhees [10] to study bimodal coarsening
in Nimonic 115. Experimental data at short aging durations behaved in
accordance with the cubic rate law that corresponded to disappearance of the fine
followed by a plateau region where the number of primary precipitates was
nearly constant. At a later stage, data again followed the cubic rate law where
coarsening was deemed to have reached steady-state. The numerical model
predicted the trends in the experimental data reasonably well, better than the
existing unimodal LSW coarsening models [7]. The present work involves
experimental studies of coarsening in the temperature range of 800 through
1000C and subsequent treatment of bimodal coarsening kinetics using a
single consistent LSW rate equation.

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Materials Characterisation V

253

2 Experimental procedure
The baseline material for coarsening studies was GTD111TM which was
solutionized at 1121C for 2h followed by an inert gas fan cool and subsequently
aged at 816C for 4h. In order to conduct careful and thorough coarsening
studies of GTD111TM, baseline specimens, 20 in number, were first examined to
obtain their key microstructural statistics, viz. secondary radius rS ' ,
secondary volume fraction f v _ S ' , tertiary radius rT '

and volume

fraction f v _ T ' . Subsequently, the baseline specimens were subjected to aging at


temperatures of T1<T2<T3<T4 in the range of 800 to 1000C up to 4000h. The
specimens were again examined after conclusion of the aging treatments to
extract the key microstructural parameters mentioned above.
The procedure for obtaining precipitate statistics comprised the sequence of
metallography, microscopy and image analysis. Specimens were polished to
mirror finish in the sequence of 220 grit diamond disc, 9m, 3m and 1m
diamond suspensions followed by colloidal silica suspension. Next, the aspolished specimens were etched using a solution comprising HCl, HNO3 and
H2O and molybdic acid reagent. This etchant provides - contrast by
preferentially dissolving the precipitate phase. Specimens were then examined
in a scanning electron microscope and representative images of the underlying
microstructure were acquired from dendritic cores. The images were then
analyzed using customized image analysis routines to gather quantitative
microstructural information.

3 Results
The baseline microstructure consisted of a bimodal distribution of cuboidal
secondary precipitates and much finer tertiary precipitates as shown in fig.
1(a). The corresponding bimodal size distribution (PSD) is shown in fig. 1(b).
The averaged baseline statistics from examination of 20 specimens are as
follows:
rS ' =266nm, f v _ S ' =37%, rT ' =34nm and f v _ T ' =4%.
The microstructures of specimens that are obtained upon aging will be
summarized next. At T1, the microstructure consisted of a bimodal distribution
after 250h of aging as seen from the micrograph in fig. 2(a). Upon further aging
to 4000h, the microstructures did not show any significant coarsening of the
secondary distribution (see fig. 2(b)); only a shape change from cuboids to
corner-rounded cuboids was noted after 2000h of aging. The number density of
tertiary precipitates decreased with progressive coarsening, also evident from the
micrographs. At T2, the tertiary distribution was only sighted at 200h (see fig.
2(a)), beyond which, the tertiary precipitates coarsened and merged with the
secondary PSD. Furthermore, shape change of the secondary precipitates from
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254 Materials Characterisation V

Figure 1:

(a) Micrograph of GTD111TM baseline specimen showing bimodal


distribution and (b) histogram of the precipitate distribution.

corner-rounded cuboids to completely rounded shapes and accompanying


coarsening was clear beyond 800h of aging. A micrograph representative of the
microstructure at 4000h is shown in fig. 2(d) where rounded shapes are
evident. The kinetics of coarsening was progressively faster at T3 and T4 due to
which, snapshots of tertiary coarsening could not be captured even at relatively
small aging durations of 100h.
A plot of the total and secondary volume fraction versus aging temperature
is shown in fig. 3 for the aged specimens and the corresponding baselines. It is
clear from the plot that f v _ tot is higher after aging, which is primarily due to
discrepancy in the secondary volume fractions before and after aging. This
unexpected rise in the volume fraction upon aging, across the temperature range
of 800 to 1000C is hard to reconcile because the thermodynamically permissible
volume fraction resulting from the standard aging treatment should be higher

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Materials Characterisation V

Figure 2:

255

Representative microstructures of specimens aged for (a) 250h at


T1, (b) 4000h at T1, (c) 200h at T2 and (d) 3200h at T2.
60
fv_Sg'agedspecimens
fv_totagedspecimens
fv_Sg'baselines

55

fv_totbaselines
fv_totTHERMOCALC

fv (%)

50

45

40

35

30
T(C)

Figure 3:

Plot of the secondary and total volume fractions in the baseline


and aged specimens at temperatures of T1<T2<T3<T4. The
expected trend in the equilibrium volume fraction (computed
using THERMOCALC) through this temperature range is also
shown.

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256 Materials Characterisation V


8
T1tertiaryg'

7
6

fvT' (%)

5
4
3
2
1
0
0

1000

2000

3000

4000

5000

t(h)

Figure 4:

Plot showing evolution of the tertiary volume fraction at T1.

600

160
T1secondaryg'
T2secondaryg'

500

T4secondaryg'

120
100

300

80

rT' (nm)

T1tertiaryg'

400

rS' (nm)

140

T3secondaryg'

60

200

40
100

20

0
0

Figure 5:

1000

2000

3000
t(h)

4000

0
5000

Plot showing evolution of the mean secondary radius with aging


through temperatures of T1 through T4 (T1<T2<T3<T4). The
variation of the mean tertiary radius at T1 is plotted on the
secondary y-axis.

than at temperatures of T2 to T4. The latter is inferred from the monotonically


decreasing trend in the THERMOCALC predicted equilibrium volume fraction
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Materials Characterisation V

257

with increasing temperature, also shown in fig. 3. The evolution of the tertiary
volume fraction upon aging at T1 is shown in fig. 4. The gradually decreasing
trend is expected for two reasons- (a) consumption of the tertiary by the
secondary during coarsening and (b) inherent coarsening of the tertiary , thus
merging with the secondary population.
Figure 5 shows a plot of the mean secondary radius versus aging time for
all the four data sets. The expected increase in rS ' due to coarsening is
preceded by a dip early on at T1, T2 and T3. The likely reason for this is
attributed to fraction of the coarser tertiary population joining into the secondary
distribution. The increase in the mean tertiary radius at T1 is also shown in the
same plot. However, the observed increase in rT ' is apparent because of the
fact that a fraction of the tertiary population is consumed during coarsening of
the secondary distribution (see fig. 4), which otherwise would have participated
in inherent coarsening of the tertiary distribution.

4 Analysis and discussion


The assumptions made for analysis of the coarsening kinetics using the results
presented in the preceding section are stated as follows:
1.

2.

3.

The baseline statistics need further validation because of the unexpected


increase in the secondary and total volume fraction upon aging, as
mentioned earlier. Therefore, coarsening analysis will be conducted using
population statistics of the aged specimens only.
The kinetics of secondary coarsening will be analyzed using unimodal
secondary statistics at T2, T3 and T4 after disappearance of the tertiary
distribution. This ensures that any effects of the tertiary distribution on
coarsening of the secondary population are no longer present. Therefore,
the commencement of coarsening ( t 0 ) is defined as the earliest aging
sampling step at which, the tertiary distribution is non-existent. Longer
aging durations are accordingly shifted as per this definition. Data at T1 is
not used for this analysis because a bimodal distribution is evidently
present up to 4000h of aging. Furthermore, the present data do not show a
clear coarsening trend in secondary size and statistics at longer aging
times must be considered for obtaining a clearer trend.
The expected rate of coarsening of the tertiary distribution at T1 should
be faster than the observed rate for reasons specified earlier. Therefore, to
arrive at the expected coarsening rate, the loss of tertiary volume
fraction between successive aging steps (see fig. 4) is reconciled and
accounted for during coarsening.

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258 Materials Characterisation V


1.E+08

T2secondaryg'observed
T3secondaryg'observed

1.E+08

T4secondaryg'observed

rt3ro3 (nm3)

8.E+07

R=0.99

6.E+07
4.E+07
R=0.93

2.E+07
R=0.99

0.E+00
0

Figure 6:

500

1000

1500
t(h)

2000

2500

3000

Cubic rate law plot of the mean secondary radius at T2, T3 and
T4 (T2<T3<T4). Data used for analyzing kinetics correspond to
unimodal secondary PSDs only.

As per assumption#2, secondary coarsening kinetics is analyzed using the


cubic rate law rSt '

rSo '

k (T )t , where rSt ' is the secondary radius at


Q

k
is the radius at t 0 and k (T ) o e RT is the coarsening rate
time t,
T
constant with pre-exponential k o and activation energy Q . A plot of the cubic
rate law at T2, T3 and T4 shows reasonably good linear fits at all the three
temperatures as shown in fig. 6. As expected and congruent with microscopic
observations, the rate of coarsening (slope of the linear fit) is enhanced with
increasing aging temperature. Next, a plot of the coarsening rate
1
constant k (T ) versus
(see fig. 7) is used to extract the activation energy of
RT
coarsening as 212.45 (kJ/mol). The expression for the rate constant describing
the secondary coarsening kinetics is as follows:

rSo '

212447

k
k (T ) o e RT
T

(nm3/h)

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(1)

Materials Characterisation V

259

18.5

k(T)(nm3/h)

18

Q=212,447kJ/mol

17.5

R=0.98

17

16.5

16
1/RT(mol/JK)

Figure 7:

1
Plot of k (T ) vs.
using the rate constants at T2, T3 and T4.
RT
The activation energy of secondary coarsening is obtained as
slope of the linear fit.

4.E+06

ObservedcoarseningrateTg'
ExpectedcoarseningrateTg'

3.E+06

PredictedcoarseningrateTg'

rt3ro3 (nm3)

3.E+06

R=1

2.E+06
R=0.98

2.E+06
1.E+06
5.E+05
R=0.80

0.E+00
0

Figure 8:

500

1000

1500

2000
t(h)

2500

3000

3500

4000

Cubic rate law plots of the mean tertiary radius at T1 shown for
three cases measured data, predicted dataset using secondary
kinetics and expected dataset by correcting for volume fraction loss
of tertiary during coarsening.

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260 Materials Characterisation V


Next, this rate constant equation is used to predict coarsening of the tertiary
distribution at T1 starting at 250h. However, realizing that eqn. (1) represents
coarsening rate of the secondary distribution with a volume fraction of ~0.45,
the enhanced coarsening rate due to high volume fraction [3,11,12] must be
accounted for prior to applying the rate equation to the tertiary distribution. The
pre-exponential in eqn. (1) is divided by a scaling factor k ( f v ) 3.5 to correct for
volume fraction effects on coarsening [3]. The resulting equation for the rate
constant, listed below, may then be applied to coarsening under low volume
fraction scenario such as tertiary coarsening.
212447

0.29 k o RT
k (T )
e
T
3

Figure 8 shows a plot of rTt '

rTo '

(nm3/h)

(2)

vs. t for tertiary coarsening at T1

and the corresponding linear fits for three cases (a) observed using measured
data, (b) predicted using eqn. (2) and (c) expected by correcting measured
data. The aging duration of 250h is taken to be the starting point i.e. t 0 and the
corresponding tertiary statistics are used to generate the predicted data set. The
expected tertiary radii are computed in accordance with assumption#3 by the
t

t
following procedure. Denote f v N_ T ' , N v N_ T ' and rTN'

to be the volume

fraction, particle density (number of precipitates per unit volume) and mean
radius of the tertiary distribution at the Nth aging time step corresponding to
time t t N . It should be noted that the data point at 250h is denoted using the
superscript t o ( t o 0 in this case) and longer aging times are scaled with

reference to 250h as the starting point. Now, f v N_ T1 ' f v N_ T ' is the tertiary
volume fraction which is consumed during secondary coarsening. This lost
fraction between successive time steps is accounted for to obtain the expected

radii. Specifically, the lost volume fraction f v N_ T1 ' f v N_ T '

results in a

volume V t N 1 t N over and above the volume VTN' of a tertiary precipitate


t

with mean size rTtN' . The quantities VTtN' and V t N 1 t N are defined as
below:
t

VTN'
and
V

t N 1 t N

3
4
rTtN'
3

t N 1
tN
v _ T ' f v _ T '
t
N v N_ T '

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(3)

(4)

Materials Characterisation V

261

Here N v N_ T ' is the number density of tertiary precipitates at the


instant t t N . Using this framework, the expected mean tertiary radius
t

N
rexp
ected _ T ' at t t N is computed as:

N
3
tN
t
t
VT ' V N 1 N
tN
1

(5)
rexp
ected _ T '
4

The correlation coefficient of the linear fit is improved from 0.8 for the
measured data to 0.98 (see fig. 8) for the expected data set by making this
correction. The agreement between the coarsening rate constants of the
expected and predicted datasets is also better when compared to the rate
constant of the measured dataset. The reasons for disparity between the rate
constants of the expected and predicted data sets could be two fold. First,
there could be errors associated with truncation of the tertiary PSD due to
overlap of the secondary and tertiary distributions, as is the case at 1000 and
2000h at T1. Secondly, any variations in the precipitate statistics that exist
among the baselines are ignored in the present analysis. It is quite possible that
the truncation errors and initial baseline variations could lead to errors in
estimation based on eqn. (5).

5 Conclusions
Aging experiments were conducted on GTD111TM in the temperature range of
800 to 1000C with the objective of studying bimodal coarsening kinetics in
this alloy. Secondary coarsening kinetics elucidated using data where the
PSDs were clearly unimodal yielded an activation energy of 212.45 (kJ/mol).
This kinetics was then applied to tertiary coarsening at the lowest aging
temperature by using an appropriate scaling factor to discount volume fraction
enhancement of coarsening. Separately, the kinetics of the measured data was
corrected approximately by accounting for volume fraction loss of tertiary
between successive aging steps accompanying secondary coarsening. The
coarsening rate constants obtained from these two approaches showed a
reasonable agreement with each other. Thus, the kinetics of bimodal
coarsening in GTD111TM could be described using a single consistent LSW rate
equation in the chosen range of temperatures.

Acknowledgements
The authors greatly appreciate S. Vipin for careful metallographic preparation of
GTD111TM aged specimens. Next, we would like to acknowledge the staff at the
National Metallurgical Laboratory, Jamshedpur, India for their assistance in
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262 Materials Characterisation V


characterization of the baseline GTD111TM specimens. We also acknowledge the
helpful discussions with Drs. M. Karadge and S. Swaminathan on treatment of
coarsening data.

References
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[2] Sims, C. T. and Hagel, W. C. The Superalloys. New York : John Wiley &
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[5] Mastromatteo, F., Niccolai F., Giannozzi, M. and Bardi, U., The coarsening
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[8] Kelekanjeri, V. S. K. G., Moss, L. K., Gerhardt, R. A. and Ilavsky,
J., Quantification of the coarsening kinetics of precipitates in Waspaloy
microstructures with different prior homogenizing treatments. Acta
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[9] Sharghi-Moshatghin, R and Asgari, S., The effect of thermal exposure on
the characteristics in a Ni-base superalloy. Journal of Alloys and
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[10] Chen, M. K. and Voorhees, P. W., The dynamics of transient Ostwald
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Materials Characterisation V

263

Effect of the elastomer stiffness and


coupling agents on rheological properties
of magnetorheological elastomers
A. Boczkowska & S. F. Awietjan
Faculty of Materials Science and Engineering,
Warsaw University of Technology, Poland

Abstract
The reported studies are related to a new group of intelligent materials, such as
magnetorheological elastomers (MREs), which are composites of ferromagnetic
particles embedded in elastomer matrix. Studies on fabrication of MREs were
carried out using two different polyurethane elastomers as a matrix,
ferromagnetic particles and coupling agent. The matrices were differed in
elastomer stiffness and hardness. As a ferromagnetic component carbonyliron
powder with particle size of 6-9 m was used. Particles were oriented into chains
under the external magnetic field of 240 kA/m. Samples with anisotropic
particles arrangement and particles volume fraction equal to 11.5% were
examined. Microstructure of MREs was observed using Scanning Electron
Microscopy. Structural and magnetic anisotropy of the MREs was derived from
the magnetic studies. Rheological properties of the MREs, such as storage and
loss modulus and loss factor, were characterized as a function of shear frequency
and strength of the magnetic field. Absolute and relative magnetorheological
effects were calculated taking the microstructure into account, which was formed
in the course of the MRE fabrication, by changing the elastomer type and
application of the coupling agent. As a result of the studies it was found that the
MREs with stiffer matrix exhibit much lower MR effect than the soft ones. Also
the application of coupling agent lead to a decrease of MR effect by the
formation of bound elastomer surrounding the particles, which increases the
stiffness of the matrix.
Keywords: magnetorheological elastomers, polyurethanes, carbonyl iron,
rheological properties, coupling agents, microstructure, magnetic properties,
magnetorheological effect.
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264 Materials Characterisation V

1 Introduction
Magnetorheological elastomers (MREs) are composites of ferromagnetic
particles embedded in elastomer matrix. They belong to a new group of
intelligent materials, which change their rheological properties under the
influence of an applied magnetic field. They are solid analogues of the
magnetorheological fluids (MRF) where the matrix is a solid elastic polymer
rather than carrier oil. These both consist of micrometer-sized magnetically
permeable particles in a non-magnetic matrix material. As in the case of MRF,
the particles try to arrange themselves in the direction of the magnetic field. An
external magnetic field is applied during the curing process of the elastomer,
what is described in many papers, e.g. Zhou [1], Farshad and Benine [2], Jolly
et al. [3]. The field induces dipole moments within the particles, which seek
minimum energy states. Chains of particles with collinear dipole moments are
formed and curing of the polymeric matrix locks the chains in place. As a result
special structures, such as chains or columns of particles, remain in the matrix.
MREs have controllable magnetic field dependent modulus rather than field
dependent yield stress and also stable performance. The advantage of MREs, in
comparison to MRF, is that ferromagnetic particles do not undergo the
sedimentation. Moreover, the amount of filler is usually lower in MREs. As a
result, the weight of sensing and actuating devices based on MREs is reduced
and due to their microstructure, the time, following signal introduction, for a
strain change response to applying a magnetic field is shortened, as it was
described by Carlson and Jolly [4]. MREs exhibit reversible changes of their
properties and shape under the magnetic field, what makes them attractive for
applications as dampers, sensors or actuators, e.g. An and Shaw [5], Farshad and
Le Roux [6]. The automotive bushing based on MREs, adjusted to reduce
suspension deflection and to improve passenger comfort, were patented by
Watson [7] and Steward et al. [8] for Ford Motor Company.
The magnetic particles are usually carbonyl iron and as the matrix soft
silicone elastomers, poly(vinyl alcohol), gelatine, natural rubber or polyurethanes
can be used. The results of the studies presented in the literature [912] show
that the properties of MREs depend on the particles shape, size and volume
fraction, as well as the magnetic field strength. Only a few papers are focused on
the influence of the polymer matrix properties on the magnetorheological effect
(MR effect) in MREs. Gong et al. [13] and Lokander and Stenberg [9] reported
the advantageously influence on the MR effect of the addition of plasticizers to
the silicon rubber due to the decrease of the polymer matrix stiffness. Jiang et al.
[14] indicate on the positive effect of the particles surface modification on the
increase of the MR effect, while Zhang et al. [15], Fan et al. [16] and Li et al.
[17] show that the enhancement of the particle-polymer matrix interaction leads
to the decrease of MR effect due to the existence of bound-rubber phenomenon.
The improvement of filler-matrix interaction is an effective way to improve the
mechanical properties of materials; however in the case of MREs it can affect the
MR effect.

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In our studies the influence of the matrix and the interaction between matrix
and filler on the MREs properties were investigated. We used two polyurethane
elastomers as a matrix, which were differed in stiffness and hardness. Particles
were oriented into chains under the external magnetic field of 240 kA/m.
Samples with the same particles volume fraction equal to 11.5%, were examined.
The iron particles-polyurethane matrix interactions were changed by the
application of silane coupling agent and the effect of the interaction on the
performance of MREs were investigated. Rheological properties of the MREs,
such as storage and loss modules and loss factor, were characterized as a
function of shear frequency and strength of the magnetic field. Absolute and
relative MR effects were calculated taking microstructure into account, which
was formed in the course the MREs fabrication, by changing the elastomer type
and application of the coupling agent.

2 Materials and methods


Magnetorheological elastomers were manufactured using:
soft polyurethane (PU), obtained from polyether polyols VORALUX
HF 505 used in a blend with 14922, with the average molecular weight
respectively 3596 and 4350 g/mol, and isocyanate compound HB 6013,
supplied by Dow Chemical Company,
segmented urea-urethane elastomer (EPU), obtained from 4,4diphenylmethane diisocyanate (MDI), ethylene oligoadipate (OAE)
with the average molecular weight about 2000 g/mol and dicyandiamide
(DCDA) as a chain extender.
PU substrates were mixed in the weight ratio, respectively 30:70:23. Mixing
and curing process were conducted at room temperature.
EPU with molar ratio of MDI:(OAE+DCDA) equal to 2.5 was synthesized by
one-shot method. The curing process was carried out at temperature of 150oC,
what makes technology aspects of MRE manufacturing more complicated. The
existence in every short hard segment of strong polar urea group and strong polar
nitrilimide side-group increases the urea-urethane thermal and mechanical
properties, as well as stiffness and hardness in comparison to soft polyether
polyurethane (see Table 1).
The ferromagnetic component used in the MREs, was carbonyliron powder
with particles size ranging from 6-9m, produced by Fluka. The amount of the
carbonyl-iron particles was equal to 11.5 vol.%. It was found in our earlier
studies, e.g. Boczkowska and Awietjan [18], carried out for the series of samples
with the particles content varied from 1.5 to 33 vol.%, that the highest structural
and magnetic anisotropy, as well as MR effect was observed for MREs
containing 11.5 vol.% of carbonyl-iron. Therefore, in this study such volume
fraction of particles was used.
As shown in Table 1 polyurethane PU 70/30 is characterized by lower density
and mechanical properties than EPU 2.5. Low hardness and stiffness of the
polyurethane matrix can lead to the higher relative property changes of the MRE
under an external magnetic field. On the other hand, the EPU 2.5 is distinguished
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266 Materials Characterisation V


by lower viscosity of reactive mixture of substrates and good mechanical
properties. Low viscosity during the processing of the MRE makes the
arrangement of the particles into aligned chains very easy.
Table 1:

Selected physical and mechanical properties of elastomers used for


MREs fabrication.

Material

Viscosity
(mPas)

Density
(g/cm3)

PU 70/30
EPU 2.5

8000
1400

1.03
1.26

Glass transition
temperature (oC)
Soft
Hard
segments segments
-64
41
-23
165

Hardness
(oShA)

Youngs
modulus
(MPa)

< 10
87

0.1
14

The samples were subjected to a magnetic field during curing to produce


aligned carbonyl-iron chains within the elastomer. The magnetic field strength
used during MREs processing was equal to 240 kA/m. Samples prepared for
rheological measurements were in the form of 2 mm thick and 20 mm in
diameter round plates.
As a coupling agent N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (U-15)
was used with the chemical formula H2NCH2CH2CH2Si(OC2H5)3, supplied by
Unisil Tarnow Company. Carbonyl-iron particles were mechanically stirred in
the 1% solution of coupling agent in toluene before MREs fabrication, until the
solvent evaporation.
The microstructure of cross-sections of MREs was observed using scanning
electron microscopy (SEM) Hitachi S-2600. The smooth surfaces were cut on
Rotary Microtome LEICA RM2165 with LN21 cooling device.
Magnetic properties were studied by Lake Shore vibrating sample
magnetometer (VSM). Tests were carried out parallel and perpendicular to the
direction of particles alignment, corresponding to the magnetic field direction
during curing.
Rheological properties were evaluated at 25oC with the application of Ares
Rheometer from TA Instruments with plate-plate setup (plate diameter - 20 mm,
gap - 2 mm, magnetic field ranged from 0 to 480kA/m). The chains of particles
were aligned parallel to the magnetic field direction during experiment in the
case of investigation of the influence of the matrix properties or they were sloped
to 45 degrees in the case of the examination of the influence of coupling agent.

3 Results and discussion


3.1 Microstructure observations
Microstructure observations by SEM proved the existence of aligned particles
chains in the direction of the magnetic field applied during curing of the matrix
in PU 70/30 polyurethane soft elastomer (fig. 1a), as well as in EPU 2.5 ureaurethane elastomer (fig. 1b). The direction of the magnetic field during curing is
shown by the white arrows in figs. 1a, 1b.
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a)

b)

Figure 1:

SEM images of the cross sections of MREs with 11.5 vol.% of


particles, obtained from elastomers: a) PU 70/30 polyurethane,
b) EPU 2.5 poly(urea-urethane).

Although the viscosity and the chemical composition of the reactive mixtures
of substrates are different, the alignment of particles into chains in both cases
was obtained. The average distance among the chains of particles calculated
using image analysis, as described in Boczkowska et al. [19], is equal to 404
m.
3.2 Magnetic measurements
The existence of structural and magnetic anisotropy was confirmed by VSM
studies. Tests were carried out parallel (II) and perpendicular (L) to the direction
of particles chains, corresponding to the magnetic field direction during curing.

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268 Materials Characterisation V


a)
80

II
60

Magnetization [Am2/kg]

40
20
0

-800

-600

-400

-200
0
-20

200

400

600

800

-40
-60
-80
Magnetic field [kA/m]

b)
150

Magnetization [Am2/kg]

II
L

100
50
0

-800

-600

-400

-200
0
-50

200

400

600

800

-100
-150
Magnetic field [kA/m]

Figure 2:

Hysteresis loops for MREs with 11.5 vol.% of particles obtained


from elastomers: a) PU 70/30 polyurethane, b) EPU 2.5 poly(ureaurethane).

In fig. 2 hysteresis loops obtained for the MREs with different matrix material
are shown. From the hysteresis loops the anisotropy coefficient (Ab) was
calculated at the selected value of magnetic field strength of 160 kA/m. It is
expressed by the ratio of magnetization measured at 160 kA/m, respectively
parallel and perpendicular to the particles alignment direction. The Ab values are
similar for both kind of MREs matrix. They are equal to 1.50 for PU 70/30 and
1.42 for EPU 2.5, what means that the difference in viscosity and the chemical
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Materials Characterisation V

269

composition of the reactive mixtures of substrates for both elastomers do not


significantly influence on the possibility of particles to arrange themselves along
the magnetic field direction.
3.3 Rheological properties
In this study such rheological properties as storage modulus (G), loss modulus
(G) and a ratio of G to G, so called loss angle, were measured as a function of
oscillation frequency and the magnetic field strength.
In viscoelastic materials, some of the deformation energy is stored and
recovered during each cycle and some is dissipated as heat. The storage modulus
represents the capacity of the material to store the energy of deformation, which
contributes to the material stiffness. The loss modulus represents the capacity of
the material to dissipate the energy of deformation into heat. Loss angle is a
measure of material damping properties.
Rheological studies were carried out for the MRE samples fabricated using
PU 70/30 elastomer without and with U-15 coupling agent. Also the influence of
the matrix hardness and stiffness on rheological properties was investigated for
PU 70/30 and EPU 2.5 elastomers. The examples of G, G and tan curves for
the MREs based on PU 70/30, obtained without and with coupling agent, as a
function of the oscillation frequency, for different magnetic field strengths are
shown in fig. 3.
Storage and loss modulus grow as a function of oscillation frequency. The
values of G and G increase with the increase of the magnetic field strength.
The values of G and G for MREs without coupling agent measured without
magnetic field exhibit the lowest course, what means that such samples are
characterized by lower stiffness than the samples with coupling agent.
The improvement of the adhesion between iron particles and polyurethane
matrix leads to the immobilizing of the macromolecules around the particles,
what increases the stiffness of the polyurethane in the area surrounding the
particles. On the other hand MREs with coupling agent exhibit higher values of
loss angle what is a measure of damping properties. The higher values of tan
mean that the better are the damping properties of such material. Loss angle
increases with the increase of the magnetic field strength, and the highest values
were obtained for MREs with coupling agent. However, significantly higher
growth in G and G under the magnetic field was observed for the samples
without coupling agent.
Absolute (G) and relative (G/G0) magnetorheological effects were
calculated from rheological curves shown in fig. 3, for the same selected
frequency equal to 10 Hz. The results have been presented in fig. 4 as a function
of the magnetic field strength, where G0 is the zero field modulus that means
the storage modulus obtained without magnetic field.

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270 Materials Characterisation V


11,5%Fe 0 kA/m
11,5%Fe 160 kA/m
11,5%Fe 480 kA/m
11,5%Fe+1%U-15 80 kA/m
11,5%Fe+1%U-15 320 kA/m

0.90
0.80

GI [MPa]

0.70

11,5%Fe 80 kA/m
11,5%Fe 320 kA/m
11,5%Fe+1%U-15 0 kA/m
11,5%Fe+1%U-15 160 kA/m
11,5%Fe+1%U-15 480 kA/m

0.60
0.50
0.40
0.30
0.20
0.10
0.00
0.1
0.16

f [Hz]

10

100

f [Hz]

10

100

11,5%Fe 0 kA/m
11,5%Fe 80 kA/m
11,5%Fe 160 kA/m
11,5%Fe 320 kA/m
11,5%Fe 480 kA/m
11,5%Fe+1%U-15 0 kA/m
11,5%Fe+1%U-15 80 kA/m
11,5%Fe+1%U-15 160 kA/m

0.14
0.12

GII [MPa]

0.10
0.08
0.06
0.04
0.02
0.00
0.1

0.35
0.3

tan

0.25
0.2
0.15
0.1

11,5%Fe 0 kA/m
11,5%Fe 160 kA/m
11,5%Fe 480 kA/m
11,5%Fe+1%U-15 80 kA/m
11,5%Fe+1%U-15 320 kA/m

0.05
0
0.1

Figure 3:

f [Hz]

11,5%Fe 80 kA/m
11,5%Fe 320 kA/m
11,5%Fe+1%U-15 0 kA/m
11,5%Fe+1%U-15 160 kA/m
11,5%Fe+1%U-15 480 kA/m

10

100

Changes of storage (G), loss (G) modulus and loss angle (tan )
as a function of frequency under magnetic field of 0, 80, 160, 320,
480 kA/m.

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Materials Characterisation V

271

0.70
0%U-15
0.60

1%U-15

G' [MPa]

0.50
0.40
0.30
0.20
0.10
0.00
0

80

160

240

320

400

480

400

480

560

H [kA/m]
800
0%U-15

700

1%U-15

G'/G'0 [%]

600
500
400
300
200
100
0
0

Figure 4:

80

160

240

320

H [kA/m]

560

Absolute (G) and relative (G/G0) MR effects of the MREs


based on PU 70/30 obtained without and with the silane coupling
agent vs. the magnetic field strength (H).

Both MR effects, absolute and relative, grow with the magnetic field growth.
The significant difference is observed between samples fabricated with and
without application of silane coupling agent. The difference is much more
significant with the magnetic field growth. The MR effect is higher in the MREs
obtained without the application of the coupling agent because of the lower
stiffness of the polyurethane matrix, what makes the ferromagnetic particles
easier to attract under the magnetic field and as a result to introduce the
additional strain and stress to the polyurethane matrix.
Similar results were obtained for MREs fabricated from elastomers with
different stiffness and hardness, as shown in fig. 6.
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272 Materials Characterisation V

0.30
PU 70/30
0.25

EPU 2,5

G' [MPa]

0.20
0.15
0.10
0.05
0.00
0

80

160

240

320

400

480

560

400

480

560

H [kA/m]
600
PU 70/30
500

EPU 2,5

G'/G'0 [%]

400
300
200
100
0
0

80

160

240

320

H [kA/m]

Figure 5:

Absolute and relative MR effect of the MREs based on PU 70/30


and EPU 2.5 elastomers vs. the magnetic field strength (H).

MREs with the stiffer matrix (EPU 2.5) exhibit significant lower MR effect
because the stiffer matrix makes impossible the particles to displace when they
are subjected to the magnetic field.

4 Conclusions
The properties of the MREs elastomeric matrix have a great influence on their
rheological properties. Elastomer with higher stiffness and hardness leads to the
higher storage and loss modulus of the MREs measured without magnetic field,
while under the magnetic field the values are significant lower in comparison to

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Materials Characterisation V

273

MREs obtained from soft elastomer. As a result the absolute and relative MR
effect is much higher in MREs obtained from soft elastomer.
The highest absolute and relative MR effect was obtained for the MREs
synthesized from PU 70/30 elastomer with 11.5 vol.% of carbonyl-iron particles.
The values of MR effects under the magnetic field of 480 kA/m reached 0.27
MPa and 540%, respectively, when the particles chains were aligned parallel to
the magnetic field direction or 0.52 MPa and 750%, when the chains of particles
were sloped to 45 degrees. The influence of the particles chains arrangement on
the rheological properties is the subject of our different study.
The increasing of the adhesion between particles and polyurethane matrix
leads to the significant decrease in the MR effect by the existence of bound
elastomer around the particles, what makes the matrix stiffer. High stiffness of
the MREs matrix do not allow for the particles displacement under the magnetic
field and subsequently the deformation of the elastomeric matrix.
The rheological properties of MREs depend also on the oscillation frequency
and magnetic field strength.

Acknowledgement
This work was financed by National Centre for Research and Development
(Poland) as a grant no. NR 15 0010 04.

References
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[2] Farshad M. and Benine A., Magnetoactive elastomer composites, Polymer
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[3] Jolly M. R., Carlson J.D., Munoz B.C. and Bullions T.A., The
Magnetoviscoelastic Response of Elastomer Composite Consisting of
Ferrous Particles Embedded in a Polymer Matrix, Journal of Intelligent
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suspension bushing, US Patent 5.609.353, 1997.
[8] Stewart W. M., Ginder J. M., Elie L. D., Nicholls M. E., Method and
apparatus for reducing brake shudder, US Patent 5.816.587, 1998.
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[14] Jiang W.G., Yao J.J., Gong X.L., Chen L., Enhancement in
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[15] Zhang X.Z., Gong X.L., Zhang P.Q, Li W.H., Existence of Bound-Rubber
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Chinese Journal of Chemical Physics, 20(2), pp. 173-179, 2007.
[16] Fan Y.C., Gong X.L., Jiang W.Q., Zhang W., Wei B., Effect of maleic
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[17] Li J., Gong X., Zhu H., Jiang W., Influence of particle coating on dynamic
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[18] Boczkowska A., Awietjan S.F., Urethane Magnetorheological Elastomers
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Materials Characterisation V

275

Optimization of magnetoelastic properties of


pure nickel by means of heat treatments
A. L. Morales, A. J. Nieto, J. M. Chicharro, P. Pintado,
G. P. Rodrguez & G. Herranz
Department of Applied Mechanics and Project Engineering, ETSII,
University of Castilla, La Mancha, Spain

Abstract
In this work we include valuable information about the way in which nickel may
become a valuable smart material for some applications and we provide a better
understanding of the influence of internal stresses on its magnetoelastic effects.
The different states of internal stress are achieved via different heat treatments
obtained by modifying three main parameters: the heating temperature, the heating
time and the cooling method. Then, we carried out the next works: first, a
microscopic analysis of the grain size of the samples under different heat
treatments; second, all the tested specimens were subjected to an exhaustive
internal stress analysis via X-Ray diffraction techniques; and third, the E- and
-effects were estimated in order to link the internal stress state of the sample to
its magnetoelastic response. The results can guide us in selecting the most suitable
heat treatment in order to make nickel show the smart properties we desire.
Keywords: magnetoelasticity, internal stress, heat treatments, nickel, X-Ray
diffraction.

1 Introduction
Magnetomechanical materials are a kind of smart material in which there is a
reciprocal coupling between their mechanical and magnetic properties [1]. In this
broad category, described by Jiles in [2], we can find both magnetoelastic and
magnetoplastic materials. The former are those in which the variation of the
altered properties is reversible, whereas the latter are those in which the recovery
of the properties is not necessarily obtained simply on removal of the magnetic
or mechanical action.
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276 Materials Characterisation V


Some crystalline pure nickel results about E-effect and magnetomechanical
damping were previously published in our recent work [3]. In said work, nickel
clearly stands out from the rest of classical ferromagnetic materials like iron and
cobalt, but yet without showing enough variations to be considered a suitable
choice for any application. A bit later, we published our work [4], which also
deals with the influence of internal stresses in the magnetoelastic behaviour of
nickel and provides a great amount of significant quantitative data related to this
topic. In the present work, not only do we want to provide further results, details
and discussions related to the microscopic and internal stress characterization of
this material, but also we include a qualitative discussion about the way in which
this comprehensive characterization can help us to optimize its magnetoelastic
response in accordance to different objective functions.
Other works such as [57] have also dealt with this topic but they considered
either different effects or different materials. In this work in particular, two
salient magnetoelastic effects will be measured in order to analyze the influence
of internal stress on magnetoelasticity in nickel: the dependence of elastic
modulus and damping on the magnetic field, i.e., the so-called E- and effects. The interested reader may find a theoretical background about these
effects and the influence of internal stress on them in several works such as [8].

2 Experimental details
Pure crystalline rods of nickel 201, all from the same molten material and
manufacturing process, were used in this work. They were 110 mm in length and
10 mm in diameter and they showed a purity level of 99.90% and a density of
8912 kg/m3.
The magnetoelastic properties were measured via a recently experimental
system which we developed in [9] and enhanced later in [3]. It is based on laser
Doppler vibrometry and it turns out to be a suitable method for measuring Eand - effects: not only is it able to measure both effects simultaneously and
accurately, but it also allows us to obtain stress- and path-dependencies.
The different heat treatments are achieved by modifying three main
parameters: the heating temperature, the heating time and the cooling method.
The selection of the different heating temperatures for our scheduled heat
treatments, probably the more significant parameter from the point of view of
internal stresses, was made in accordance with the recommendations found in
[10] for nickel specimens. This led us to three different treatments: annealing
(7051205C), designed to produce a recrystallized grain structure and softening
in work-hardened alloys; stress relieving (425870C), used to reduce stresses in
work-hardened non-age-hardenable alloys without recrystallizing the grain
structure; and stress equalizing (230315C), used to balance stresses in coldworked materials without appreciably decreasing mechanical strength. Table 1
presents a summary of the heat treatments. In it, each specimen has been
identified by three digits (which represent the heating temperature in Celsius),
two digits (which indicate the heating time in hours) and one letter (which refers

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277

to the cooling method, i.e., water, air or furnace). The initial state of the nickel
specimens is labelled AR (as received).
Finally we want to emphasize that, leaving aside field-dependence, other
influences such as stress-dependence and path-dependence must be considered in
our measurements [3]. In order to avoid their influences, we will report only
those results which were obtained under 0.50 MPa and following a
magnetization path from the state of zero retentivity (Mr0) to the state of positive
saturation magnetization (Ms+).
Table 1:
Specimen
0
1
2
3
4
5
6
7
8
9
10
11
12
13

Heating
temp. (C)
300
300
600
600
900
900
900
900
900
900
900
900
900

Scheduled heat treatments.


Heating time
(h)
2
2
2
2
2
2
2
4
4
4
8
8
8

Cooling
method
Water
Air
Water
Air
Water
Air
Furnace
Water
Air
Furnace
Water
Air
Furnace

Nomenclature
AR
300-02-W
300-02-A
600-02-W
600-02-A
900-02-W
900-02-A
900-02-F
900-04-W
900-04-A
900-04-F
900-08-W
900-08-A
900-08-F

3 Results and discussion


3.1 Microscopic analysis of grain size
The scheduled heat treatments were carried out in a Carbolite Eurotherm 2416
furnace. The preparation procedure for microscopic examination of the
specimens was made in accordance to [11]. In particular, the specimens were cut
with a precision Struers Secotom-10 saw, then mounted in a hard epoxy resin
with a Struers LaboPress-3 mounting press and finally ground and polished in a
Struers TegraSystem machine (TegraPol-15 and TegraForce-1). The etchant
applied to the surfaces was a fresh solution of one part HNO3 and one part acetic
acid (glacial), which is the recommended etchant for revealing grain boundaries
in nickel 201. For the microscopic examination, the equipment used was a Leica
DM IRM inverted research microscope with a Leica DFC 480 high performance
digital FireWire camera system which allowed us to obtain micrographies and
estimations of the grain size in each specimen. Fig. 1 shows the micrographies
for the 8 most significant specimens.

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278 Materials Characterisation V

Figure 1:

Micrographies of specimens (a) AR, (b) 300-02-W, (c) 300-02-A,


(d) 600-02-W, (e) 600-02-A, (f) 900-02-W, (g) 900-02-F and (h)
900-08-W.

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On the one hand, specimens which were subjected to stress relieving (300-02W and 300-02-A) and stress equalizing (600-02-W and 600-02-A) processes
show a grain size similar to that of specimen AR. This fact agrees with the fact
that stress relieving and stress equalizing reduce and balance stresses without
recrystallizing the grain structure. Besides, in spite of small variations, we can
also observe higher grains in specimens which were subjected to stress
equalizing due to the higher heating temperature and consequently the higher
grain boundary diffusion. On the other hand, annealed specimens (900-02-W,
900-02-F and 900-08-W) clearly shows much larger grains, which will translate
into lower internal stresses. Specimen 900-08-F has not been shown because it
has got almost the same distribution of grains due to the long heating time, which
means high grain boundary diffusion even when cooled in water. Furthermore,
the concentration of small grains which appears in specimen 900-02-W
corresponds to the centre of the specimen, where the heating time was not high
enough to continue increasing the size of inner grains (the diffusion processes
goes from the outside to the inside of the rod).
Table 2:
Specimen
AR
300-02-W
300-02-A
600-02-W
600-02-A
900-02-W
900-02-A
900-02-F
900-04-W
900-04-A
900-04-F
900-08-W
900-08-A
900-08-F

Microscopic measurements.

Small grains
Perim.
Area
(m)
(m2)
350
8200
440
11900
520
14400
600
16900
700
21500
530
16600
620
20700
620
23600
-

Medium grains
Perim.
Area
(m)
(m2)
1240
41000
1240
53000
1720
144000
1730
157000
1660
147000
1640
137000
1820
167000
1750
143000
1960
194000
1900
195000
1870
170000

Large grains
Perim.
Area
(m)
(m2)
4000
590000
4200
510000
4100
650000
4200
670000
4400
670000
4700
660000
5300
780000
5300
720000
5600
940000

Table 2 shows the measurements of grain perimeter and grain area for each
specimen. The results seemed to indicate the existence of three different
distributions: small grains, with a perimeter lower than 1000 mm; medium
grains, with a perimeter between 1000 and 3000 mm; and large grains, with a
perimeter greater than 3000 mm. Specimens AR, 300-02-W and 300-02-A only
contain small grains, although perimeters and areas increase slightly when the
specimens have been heated. Specimens 600-02-W and 600-02-A show small
grains mainly although medium grains are not uncommon. Finally, all specimens
heated to 900C show large distributions of medium and large grains due to
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280 Materials Characterisation V


recrystallization, whereas small grains tend to disappear (apart from the
previously mentioned significant distribution of small grains in the centre of the
section of specimens which were subjected to a time of only 2 hours). In general,
the grain size increases with heating time and decreases with cooling velocity.
3.2 Internal stress analysis
Internal or residual stress is an extrinsic property which cannot be measured
directly but through the previous measurement of an intrinsic property of the
material. In this particular case, we have used the strain in the crystal lattice as
the intrinsic variable which will allow us to estimate the residual stresses of our
specimens. Among all the ways to measure the strain in the crystal lattice, the XRay diffraction technique clearly stands out.
X-Ray diffraction techniques can be used to determine both macroscopic
(homogeneous) and microscopic (inhomogeneous) residual stresses [12, 13]. In
this work we only take into account microstresses, which are those involved in
cold-work, plastic strains or heat treatments and lead to the accumulation of a
residual dislocation network, producing inhomogeneous strain and an
irreversible broadening of the Bragg peaks in X-Ray diffraction. Indeed, the
measurement of said broadening of the diffraction peak will be used to estimate
the internal stresses of our specimens.
Strictly speaking, we have used the WilliamsonHall method [12], which has
proven its validity to estimate residual microstresses remaining in materials after
heat treatments [13]. The X-Ray diffraction profiles (intensity vs. angle of
diffraction) have been recorded using a PHILIPS XPert MPD X-Ray
diffractometer with CuKa radiation (wavelength =1,5405) and varying the
angle of diffraction () from 40 to 100 with a scan step of 0.04 and a time per
step of 5 seconds. Fig. 2 and Fig. 3 show, respectively, the X-Ray full diffraction
profile for the specimen AR and the fitting procedure of one peak of the X-Ray
diffraction profile for the specimen 900-02-W. No other plots are included since
the peaks position in all the specimens remain the same and the variation in
width is not high enough to be easily noticed at a glance.
The width of a peak can be calculated via two different ways: as the integral
breadth , defined as the width of a rectangle having the same area and height as
the observed line profile, or as the full width at half maximum FWHM.
WinPLOTR software allowed us to obtain both of them for several reflections as
a measure of the peak width, but we only used the integral breadth in our
estimations. The strain calculated using WinPLOTR is the so-called maximum
strain.
Besides, a diffraction pattern has contributions from the instrument optics
(even a perfect sample will give lines of finite width), from particle size and
from microstrain. The way in which these contributions are added depends on
the shape of the peak. In our case, we assume that peaks are Lorentzian in shape,
so all these contributions can be directly added:
(1)

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Materials Characterisation V

281

Figure 2:

X-Ray diffraction profile for the specimen AR obtained in the


software WinPLOTR.

Figure 3:

Detail of the second peak of the X-Ray diffraction profile for the
specimen 900-02-W and the fitting procedure in WinPLOTR.

Now, considering that we can make the correction for the instrumental
broadening, the corrected integral breath due to microstrain and particle size can
be written as follows:
.

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(2)

282 Materials Characterisation V

Figure 4:

Williamson-Hall plots of specimens AR, 300-02-W, 600-02-A and


900-08-F.

where the first addend is the particle size contribution and the second addend is
the strain () contribution. Then, left-multiplying by cos we obtain:
cos

4 sin

(3)

This expression leads to the well-known Williamson-Hall plot [12], which is


the plot of cos against sin. Thus, the strain is directly related to the slope of
said plot. Fig. 4 shows some selected Williamson-Hall plots.
Table 3 gathers all the internal stresses obtained from the WilliamsonHall
plots. In addition, microstrain, demagnetized elastic modulus and lattice
parameter have been also included, this latter being known very easily once we
know the wavelength of the radiation and the angle of diffraction of each peak.
Regarding internal stresses, results provided in Table 3 are in good agreement
with what one would expect given the heat treatments carried out. Indeed, we
can distinguish three different ranges of residual stresses:
High residual stresses (over 500 MPa). These values are shown by the
specimens which were subjected to stress equalizing (230315C and
air or furnace cooling [10]). Water quenching was also tested obtaining,
as expected, the highest value.
Medium residual stresses (between 300 and 500 MPa). These values
correspond to the specimen AR and to those which have been subjected
to stress relieving treatments (425870C and air or furnace cooling
[10]). As the name of the treatment indicates, a small stress reduction is
achieved.
Low residual stresses (below 300 MPa). These values are shown by
samples that have been subjected to annealing process (7051205C and
air or furnace cooling [10]). In these cases, a high reduction of internal
stresses is achieved. Nevertheless, if water quenching is applied, the
internal stresses jump into a level of medium stresses.
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Materials Characterisation V

283

Regarding the lattice parameter, no significant variations were found, but the
obtained value is in good agreement with the typical values of the lattice
parameter in nickel samples (around 3.5 ).
Table 3: Internal stresses and lattice parameter.
Specimen
AR
300-02-W
300-02-A
600-02-W
600-02-A
900-02-W
900-02-A
900-02-F
900-04-W
900-04-A
900-04-F
900-08-W
900-08-A
900-08-F

Internal
stress (MPa)
479.0
579.6
536.6
475.2
498.3
469.0
276.9
223.4
356.6
248.6
106.8
415.8
207.6
86.2

Microstrain
(%)
0.23
0.27
0.25
0.22
0.24
0.22
0.14
0.11
0.17
0.13
0.05
0.20
0.10
0.04

Elastic
modulus (GPa)
213
213
213
216
210
220
201
199
213
203
203
216
208
203

Lattice
parameter ()
3.53
3.53
3.53
3.53
3.53
3.53
3.54
3.53
3.54
3.54
3.54
3.52
3.53
3.53

3.3 E- and -effects


The results corresponding to the E- and -effects of the 14 nickel specimens
considered show similarities which can be summarized mainly into two different
patterns which are depicted in Fig. 5 and explained next:

Pattern I is shown by specimen AR and all those which were subjected to


heat treatments of stress relieving and stress equalizing. Indeed, specimens
subjected to a heating temperature of 900C and water cooled also may be
grouped into this patter. On the one hand, the curve of elastic modulus is
compound by an initial stage of rapid growth which belongs to the low
magnetic field range (less than 150 Oe) and a second stage of slow growth
until saturation (around 350 Oe). On the other hand, the curve of damping
shows again two stages, an initial rising stage which corresponds to the low
applied magnetic field range and the second declining stage until saturation.
In both cases, variations between the values at demagnetized and saturated
states are lower than those found in pattern II.

Pattern II is shown by the specimens which were heated up to 900C and


slowly cooled down in air or inside the furnace, so they present a very low
level of internal stresses. The elastic modulus curves show the same
behaviour as in pattern I but variations between the values at demagnetized
and saturated states are greater. As far as the damping curves are
concerned, they show a very high damping value which quickly start to
decrease until saturation without intermediate peaks.
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284 Materials Characterisation V

Figure 5:

Figure 6:

Different patterns (I: black; II: gray) of the E- and - effects.

Influence of heating time on (a) E- and (b) - effects (black:


900-02-A; dark gray: 900-04-A; light gray: 900-08-A).

Since it is not the main goal of this work, we will not include results about the
E- and - effects of each treated specimen. The interested reader may consult
such results in our work [4].
Regarding the influence of the parameters involved in the heat treatments, we
can claim than the heating temperature is the most significant parameter since
only temperatures higher than 700C (900 in our tests) may lead to a pattern II
behaviour. The cooling methods also stand out as a significant parameter since
water cooling may avoid the grain diffusion and increase internal stresses, what
would lead to a pattern I behaviour. Finally, the heating time has a very minute
influence on the magnetoelastic behaviour when using long cooling methods
such as air cooling or furnace cooling. This can be seen in Fig. 6.
Another important feature we should analyze is the influence of the heat
treatments and the internal stresses on the magnetic field from which the elastic
modulus or the magnetomechanical damping remains the same, i.e., on the
magnetic field which makes the E- and - effects saturate. We can conclude
that in all the cases the saturating magnetic field is around 350 Oe, so it does not
depend on any of the heat treatment parameters which were considered.
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4 Conclusions
The previous results can guide us in selecting the most suitable heat treatment in
order to make nickel show the smart properties we desire. It is important to
notice that the optimization will depend on the objective function we select.
Smart materials are usually required to provide a maximum variation of the
salient magnitude by supplying a minimum modification of the input. This fact,
from the point of view of a magnetoelastic material, means large variations in
applied forces, natural frequencies and damping ratios obtained via small
changes in the applied magnetic field. Nevertheless, we should not discard that,
in some cases, the objective is the opposite: to obtain a constant value of elastic
modulus and damping along a range of magnetic field as large as possible.
We can extract valuable information about the different possibilities of
optimization from Fig. 5. On the one hand, if nickel is required to act as a smart
material which provides the highest E- and - effects, then it should behave
following pattern II. In addition, the characteristic damping peak of pattern I
disappears, so we get a more predictable behaviour. Thus, in the light of section
3 results, the material should show very low internal stresses, which can be
achieved via annealing heat treatments with slow cooling velocities (900-0X-A
or 900-0X-F). On the other hand, one may need that nickel show elastic and
damping properties as constant as possible under different applied magnetic
fields. Although this behaviour cannot be perfectly fitted, it is possible to
minimize the E- and - effects by making the material follow pattern I.
Again, we know from discussion in section 3, that this means getting internal
stresses as high as possible, which can be achieved via work-hardening, stress
equalizing heat treatments and fast cooling velocities (AR, 300-0X-W).
Leaving aside optimization rules, this work also provides relevant results,
details and discussions related to the microscopic and internal stress
characterization of this material. We have carried out an in-depth material
characterization in terms of grain distribution and internal stresses when nickel
specimens are subjected to several different heat treatments. On the one hand we
have included many micrographies which help us to understand not only the way
does each heat treatment modify the grain size, but also how the grain diffusion
acts depending on the heating temperature, the heating time and the cooling
method. On the other hand we have carefully described the way we have
obtained the microstrain, internal stress and lattice parameter in all our
specimens via X-Ray diffraction and the Williamson-Hall method. All these
results agree with the fact that the internal stress decreases when we increase the
heating temperature and decrease the cooling velocity, the heating time
becoming an almost negligible parameter.

References
[1] du Trmolet de Lacheisserie, E., Magnetostriction: Theory and
Applications of Magnetoelasticity, CRC Press: Boca Raton, 1993.

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286 Materials Characterisation V


[2] Jiles, D.C., Recent advances and future directions in magnetic materials,
Acta Materialia, 51, pp. 59075939, 2003.
[3] Morales, A.L., Nieto, A.J., Chicharro, J.M. & Pintado, P., Field-dependent
elastic modulus and damping in pure iron, nickel and cobalt, Journal of
Magnetism and Magnetic Materials, 322, pp. 19521961, 2010.
[4] Morales, A.L., Nieto, A.J., Chicharro, J.M. & Pintado, P., Influence of
internal stresses on field-dependent elastic modulus and damping in pure
nickel, Journal of Magnetism and Magnetic Materials, 322, pp. 35843594,
2010.
[5] Motogi, S. & Maugin, G.A., Elastic-moduli of demagnetized
polycrystalline ferromagnets, Journal of Physics D-Applied Physics, 26, pp.
14591467, 1993.
[6] Squire, P.T., Atkinson, D., Gibbs, M.R.J. & Atalay, S., Amorphous wires
and their applications, Journal of Magnetism and Magnetic Materials, 132,
pp. 1021, 1994.
[7] Kaczkowski, Z., Magnetomechanical properties of rapidly quenched
materials, Materials Science and Engineering AStructural Materials
Properties Microstructure and Processing, 226228, pp. 614625, 1997.
[8] Bozorth, R.M., Ferromagnetism, D. van Nostrand: Toronto, 1951.
[9] Morales, A.L., Nieto, A.J., Chicharro, J.M. & Pintado, P., Automatic
measurement of field-dependent elastic modulus and damping by laser
Doppler vibrometry, Measurement Science and Technology, 19, 2008.
[10] International ASM, ASM Handbook Vol. 4Heat Treating, vol. 4, ASM
International, 1991.
[11] International ASM, ASM Handbook Vol. 9Metallography and
Microstructures, vol. 9, ASM International, 2004.
[12] Williamson, G.K. & Hall, W.H., X-Ray line broadening from filed
aluminium and wolfram, Acta Metallurgica, 1, pp. 2231, 1953.
[13] Prevy, P.S., The measurement of subsurface residual stress and cold work
distributions in nickel base alloys, ASMs Conference on Residual Stress in
Design, Process and Materials Selection, ASM International, Cincinnati
(Ohio, USA), pp. 2729, 1987.

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Materials Characterisation V

287

Nanomechanical structure-property relations


of dynamically loaded reactive powder concrete
P. G. Allison1, R. D. Moser2, M. Q. Chandler1, T. S. Rushing1,
B. A. Williams1 & T. K. Cummins1
1
2

US Army Engineer Research & Development Center, USA


Georgia Institute of Technology, USA

Abstract
Low water-to-cement ratio (w/c) reactive powder concretes (RPCs) exhibit much
higher compressive strengths compared to conventional concrete through
optimized particle packing and specialized curing regimes. The high strain-rate
impact behavior of RPCs was investigated at the macroscale. However, little
work has been done to study the fundamental material behaviors and failure
mechanisms of RPC under high strain impact and penetration loads at lower
length scales. These high strain-rate loadings have many possible effects on
RPCs at the microscale and nanoscale, including alterations in the composition
and bonding present in hydrated phases such as calcium silicate hydrate (C-S-H),
in addition to fracture and debonding. In this work, the possible chemical and
physical changes of RPCs under high strain-rate impact and penetration loads
were investigated using a novel technique wherein nanoindentation
measurements were spatially correlated with chemical composition using
electron microscopy. Results indicate that high strain-rate impacts degrade both
the elastic modulus and indentation hardness of RPCs and, in particular C-S-H,
with damage likely occurring due to microfracturing and debonding. Additional
studies will be required to better understand degradation phenomena within
C-S-H itself.
Keywords: nanoindentation, SEM, EDX, RPC, UHPC, C-S-H.

1 Introduction
Concretes and Portland cement-based materials are the most-produced manmade materials on earth, with over twenty billion tons produced per year. The
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doi:10.2495/MC110251

288 Materials Characterisation V


ubiquitous use of cementitious materials within protective infrastructures makes
quantifying the response of cementitious materials to high strain-rate penetration
and impact loads a critical need as designs become more reliant on
computational tools.
Low water-to-cement ratio (w/c) reactive powder concretes (RPCs) exhibit
superior compressive strength and ductility (when fibers are admixed) compared
to conventional concrete and is increasingly being used for high strain-rate
loading applications [1]. To fully explore the potential of this material for high
strain-rate loading applications, its fundamental failure mechanisms under
impact and penetration loads have to be investigated. RPC is a highly
heterogeneous material with a microstructure consisting of hydrated cement
paste (HCP), unhydrated cement particles, fine aggregates, potentially steel
fibers and/or polymer fibers, and pores ranging from nanometer to millimeter in
diameter [2]. The addition of pozzolanically reactive silica fume results in an
HCP comprised primarily of calcium silicate hydrate (C-S-H).
C-S-H is the most important phase of the Portland cement hydration process
and functions as the binding component that holds the various other phases of
RPC together. C-S-H consists of physically and chemically bound water in
nanometer-scale gels, bulk water in gel and capillary pores, adsorbed water on
the surfaces of gels, and may behave nano-granularly [3]. Grady [4] suggests that
C-S-H may go through chemical changes such as dehydration or vaporization
under shock impact loading. Instrumented indentation; namely nanoindentation,
techniques were used to quantify the structure-property relations of concrete at
lower length scales. Velez et al. [5] performed nanoindentation tests to quantify
the elastic modulus and hardness of synthetically manufactured Portland cement
clinker phases. Hughes and Trtik [6] used depth-sensing nanoindentation and
energy dispersive X-ray (EDX) analysis to correlate the major phase
compositions and mechanical properties of hydrated cement paste.
Ulm et al. [7] developed a novel statistical nanoindentation technique to
characterize cement paste and were able to identify the existence of two distinct
types of C-S-H, LD C-S-H and HD C-S-H. DeJong and Ulm [8] and
Constantinides and Ulm [9] used a similar approach to study the degrading
mechanisms of calcium leaching and high temperature on C-S-H. Sorelli et al.
[10] also used similar techniques to characterize the properties and volume
fraction of different phases in Ultra High Performance Concrete (UHPC). Their
research showed that UHPC with a low w/c (0.2) has a much higher volume
fraction of HD C-S-H and unhydrated clinker than LD C-S-H compared to
concrete with higher w/c.
In this work, the influence of impact loadings on the nanomechanical
properties of RPCs is investigated. Specimens were extracted for impacted and
non-impacted panels of RPC. A novel technique coupling nanoindentation with
spatially correlated scanning electron microscopy (SEM) and chemical analysis
using energy dispersive X-ray spectroscopy (EDX) was developed to
characterize damage due to high strain-rate impact loadings in the RPC panels.

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Materials Characterisation V

289

Based on the results of these studies, a possible mechanism for microstructural


damage in RPCs is proposed, and the caveats associated with the techniques
utilized are discussed.

2 Experimental procedures
2.1 Materials
An RPC mixture with a w/c of 0.2 and an unconfined compressive strength of 180
MPa was cast into panels 305-mm wide by 305-mm long and 25.4-mm thick for
ballistic impact testing. The panels were impacted by 11-mm-diameter steel
spheres at half the ballistic limit velocity, which was determined according to
MIL-STD-662 [11]. The mixing, casting, curing, and ballistic testing is detailed
in the manuscript by Rushing et al. [2].
2.2 Coupled nanoindentation and SEM/EDX analysis
Analysis of impacted and non-impacted RPC specimens was performed using a
novel technique of nanoindentation coupled with SEM imaging and EDX
chemical analysis. In this coupled method, a large number of indents are
performed over a standardized indentation grid placed on the RPC sample, after
which, each indent is spatially correlated using SEM to obtain an image and
EDX to determine the chemical composition. The resulting dataset contains the
nanomechanical properties and chemical composition along with an image at
each indentation site. This coupled method allows for improved differentiation
between the various components present in RPCs and can be used to better
correlate alterations in nanomechanical (e.g., due to impact loadings) properties
to specific microstructural features. Details on specimen preparation techniques
and experimental methods are described below.
2.2.1 Specimen preparation
Specimens were extracted from the panel in the impacted zone and a nonimpacted zone as shown in Figure 1. The center of the non-impacted location
was 38 mm from both the top edge and side of the panel. This location was
selected to minimize the potential for edge effects from casting while also
avoiding the damaged zone to the greatest extent. A 25.4-mm-diameter diamondtipped coring bit was used to core the non-impacted specimens, which were then
cast into 31.8-mm-diameter cylindrical molds using EpoHeat low-viscosity
epoxy supplied by Buehler. The impacted specimen was sectioned using an oilcooled Struers Secotom high precision cut-off saw. The cross section of the
specimen was placed into a 31.8-mm-diameter cylindrical mold and mounted in
EpoHeat epoxy from Buehler. After the epoxy fully cured, the samples were
sectioned in half by the oil-cooled cut-off saw to obtain a cross section from the
center of the panel, thus limiting any surface effects such as laitance.

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290 Materials Characterisation V

Nonimpacted
specimen
location
Line on
crater
represents
edge of
crosssection
analyzed

Impacted
specimen
location

Figure 1:

Location of impacted and non-impacted specimens removed by


coring from the low w/c RPC panel.

A Buehler Ecomet/Automet 250 automatic polishing wheel was used to


polish the extracted specimens. The polishing procedure utilized a 240-grit
diamond polishing pad at 230 RPM until the specimen was planar, followed by
an UltraPadTM with a 9-m diamond paste at 130 RPM for 5 minutes, and a third
polishing step using a TriDentTM pad with a 3-m diamond paste for 5 minutes.
These first three polishing steps used a 50:50 mixture of ethylene glycol and
ethanol for a lubricant. Final polishing utilized a ChemoMet pad with 0.05-m
alumina in ethylene glycol for 5 minutes. All steps used a force of 30 N for
polishing. Once polished, the samples were desiccated prior to indentation.
2.2.2 Nanoindentation
Polished specimens were examined using an Agilent Technologies G200
nanoindenter to probe microstructural changes across the specimens.
Indentations were performed using a pyramid-shaped diamond Berkovich
indenter with a tip radius of approximately 20 nm. Prior to each measurement, a
2nd-order area function calibration was performed using a fused silica reference
material. Load controlled indentation measurements were performed up to a
maximum load of 2 mN at a loading rate of 0.2 mN/s followed by a hold time of
5 s and a 10 s unloading period. Prior to performing the nanoindentation
experiments, each specimen was examined in the SEM to create a map of
images approximately 3 mm by 3mm near the indentation site. This map was
then used to find a desired location for the indentation grid (i.e., not containing
large voids and/or surface defects).
For each specimen, a total of 500 indents were placed with a spacing of 10
m in the X-direction and 20 m in the Y-direction. Following the indents
performed for nanomechanical measurements, 100-mN fiduciary indents were
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placed at a spacing of 245 m in the X-direction and 20 m in the Y-direction


from the first indent to aid in identifying the start, middle, and end of each line of
indents so that the indentations could be precisely located using the SEM.
Assuming a Poissons ratio of 0.2, mechanical properties such as elastic modulus
and hardness were determined for the interaction region of the indentation site
[12].
2.2.3 SEM and EDX measurements
Specimens were examined both before and after nanoindentation using an FEI
Nova NanoSEM 630 field emission SEM. This device is equipped with lowvacuum capabilities, making it ideal for examining nonconductive cement-based
materials without special sample preparation or metallic coating. Imaging was
performed at an accelerating voltage of 10 kV using a backscattered electron
(BSE) detector to reveal changes in microstructure and the distribution of phases
according to their respective densities. When examined after nanoindentation,
the map of images was used to generally locate the indentation grid, while the
fiduciary indents were used to determine the location of each line of indents such
that each indent could be correlated with a location on the image. Point chemical
analyses were also performed in conjunction with SEM imaging using a Bruker
solid-state EDX detector installed in the FEI SEM. Through proper alignment of
the indentation grid facilitated by the fiduciary indents, a standardized point
chemical analysis grid was developed that resulted in a dataset of point chemical
analyses that were spatially correlated with the location of each indent.

3 Results and discussion


The highly variable phase composition and distribution present in RPCs presents
a variety of different nanomechanical properties that were sampled during
nanoindentation measurements. Figure 2 presents the load vs. depth results of
five representative indents corresponding to a fine aggregate, an anhydrous
cement grain, C-S-H, and an aberrant test. Here, C-S-H was divided into two
phases, namely low-density (LD) and high-density (HD), which was determined
through molecular simulations and similar nanoindentation studies [9].
Of particular interest is the faulty or aberrant test result shown in Figure 2,
which defies the traditional stiffening indentation curve typical for homogenous
interaction regions but still exhibits an elastic modulus result similar to a
homogenous phase (in this case HD C-S-H). These aberrant tests may present
themselves as irregular loading and/or unloading curves (as shown in Figure 2).
In heterogeneous cement-based materials, aberrant test results may occur due to
the presence of voids, polishing defects, cracking during indentation, and as
noted more recently, composite or nanocomposite multiphase response of
material present in the interaction region of the indent [1315]. The multiphase
response of cement-based materials was a topic of recent discussion in the
literature and represents an issue that may diminish the utility of nanoindentation
as a quantitative microstructural characterization technique. Thus, it is critical to
examine each indentation curve and remove aberrant results if reliable
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292 Materials Characterisation V


quantitative information is desired. All indentation curves in the present study
were reviewed, and 8% in impacted specimens and 24% in non-impacted
specimens were deemed aberrant and removed from the dataset.
2.25

LDCSH
HDCSH
Aggregate
Cement
AberrantTest

2.00
1.75

Load(mN)

1.50
1.25
1.00
0.75
0.50
0.25
0.00
0

25

50

75

100

125

150

175

200

225

250

Depth(nm)

Figure 2:

Typical load vs. indentation depth curves for LD and HD C-S-H,


aggregate, cement, and an aberrant test result.

Figure 3 (a) illustrates a typical grid of 500 measurement indentation points


and fiduciary indents superimposed on a BSE micrograph of an RPC specimen.
Using BSE imaging, the anhydrous cement and silica fume can be seen with a
bright signature, followed by fine aggregates and silica flour, and finally by the
HCP (i.e., solid products of cement hydration with low density) and voids that
appear darkest in the image. The HCP appeared to be comprised primarily of
C-S-H, with all Ca(OH)2 likely consumed by pozzolanic reactions and
subsequently converted into C-S-H. Figures 3 (b) and (c) present contour maps
of Ca:Si ratio and elastic modulus results, respectively, corresponding to the
indentation grid shown in Figure 3 (a). A clear correlation can be observed
between the location of the various components of the RPC and their respective
composition and mechanical properties.
In addition, the benefits of using this coupled technique are also particularly
apparent when trying to differentiate between phases with similar properties. For
example, fine aggregate particles and anhydrous cement present in RPCs may
exhibit similar mechanical properties, making phase identification/quantification
from only nanoindentation results a challenging task. However, when
nanoindentation measurements are coupled with chemical composition at the
indentation site, the distinction between fine aggregates (with low Ca:Si
approaching zero) and cement (with high Ca:Si of 5 to 7) becomes clear. Similar
comparisons can be made for the various phases of cement hydration present in
the HCP.
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(a) SEM-BSE micrograph of typical RPC microstructure with measurement


indentation grid and fiduciary indents superimposed.

(b) Map of Ca:Si corresponding to indentation grid.

(c) Map of elastic modulus (GPa) corresponding to indentation grid.


Figure 3:

Typical results from coupled nanoindentation and SEM/EDX


studies performed on polished RPC specimens.

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Another feature of the nanoindentation measurements clearly shown in the
elastic modulus contour map (see Figure 3 (c)) is the gradual transition in
nanomechanical properties present at interfaces between two phases. This
behavior is likely the result of a composite response of material present within
the interaction region below each indent as discussed above.
With the aberrant results removed from the dataset, further analysis of valid
nanoindentation results was performed. Figures 4 and 5 present histograms of the
elastic modulus and hardness results of all valid indents performed on nonimpacted and impacted specimens in the present study. Results presented in
Figures 4 encompass those of anhydrous cement, siliceous fine aggregates, silica
flour, the HCP (primarily composed of C-S-H), and voids/porosity. Impacted
specimens exhibited a mean elastic modulus of 47.9 GPa compared with 76.7
GPa in non-impacted specimens. In particular, significant reductions in the
proportion of indents with elastic moduli between 60 GPa and 110 GPa was
observed in impacted specimens, a range common for silica flour and siliceous
fine aggregates [10].
22
20
NonImpacted
Impacted

18

Frequency(%)

16
14
12
10
8
6
4
2

200

190

180

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

ElasticModulus(GPa)
Figure 4:

Histogram of elastic modulus results from nanoindentation


experiments performed on non-impacted and impacted RPC
specimens.

The effect of impact (Figure 5) was much more pronounced in hardness


measurements, where a large shift in hardness from a mean of 6.3 GPa to 2.7GPa
was observed. In impacted specimens, there was a particularly high increase in
the proportion of indents with hardness between 0.5 and 1.5 GPa associated with
a reduction in the proportion of indents with hardness above 4 GPa.

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16
47.1%
14
NonImpacted
Impacted

Frequency(%)

12
10
8
6
4
2

15

14

13

12

11

10

IndentationHardness(GPa)

Figure 5:

Histogram of indentation hardness results from nanoindentation


experiments performed on non-impacted and impacted RPC
specimens.

While these nanoindentation results suggest that impact loadings have a


significant influence on both the elastic modulus and hardness of RPCs, it is
difficult to determine by what possible mechanism degradation occurs. In order
to further evaluate the possible mechanisms causing the observed degradation in
nanomechanical properties, indents likely associated with homogenous C-S-H
regions were extracted from the full dataset of non-impacted and impacted RPC
specimens. Indents identified as C-S-H were selected based on a Ca:Si between 1
and 2 (consistent with C-S-H) with an elastic modulus between 10 and 50 GPa
(range typical for LD and HD C-S-H [10, 13]. Out of each dataset,
approximately 10% of indents were deemed as homogenous C-S-H. Ca:Si ratios
of the C-S-H sub-dataset were 1.44 and 1.42 for non-impacted and impacted
specimens, respectively.
The histograms shown in Figures 6 and 7 depict the distribution in C-S-H
elastic modulus and indentation hardness for non-impacted and impacted
specimens. C-S-H present in non-impacted specimens exhibited a mean elastic
modulus of 32.5 GPa and mean indentation hardness of 1.56 GPa. C-S-H present
in impacted specimens exhibited a mean elastic modulus of 27.4 GPa and mean
indentation hardness of 0.66 GPa, with a significant increase in hardness
between 0.25 and 0.75 GPa.
These reductions in elastic modulus and, in particular, hardness in impacted
samples suggests that the C-S-H, in addition to the overall microstructure of
RPCs, is degraded under high strain-rate impact loadings. The
dehydration/vaporization mechanism proposed by DeJong and Ulm [8] was
shown as a possible deterioration mechanism resulting in decreased C-S-H
packing factors and in turn reduced elastic modulus and hardness as measured by
nanoindentation. However, unless additional secondary chemical bonding was to
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296 Materials Characterisation V


occur between C-S layers (similar to irreversible creep mechanisms [16] during
the vaporization event, it is likely that rehydration of the C-S-H would occur
slowly. Furthermore, if such bonding were to occur; densifying the C-S-H and
limiting rehydration, the elastic modulus and hardness would likely increase
rather than decrease. Based on the results presented in Figures 4 and 5, it is clear
that a majority of degradation in the full RPC indentation dataset is associated
with reductions in elastic modulus and hardness associated with inert particles
and unhydrated cement. Therefore, it is likely that a majority of degradation in
RPCs following impact loading results from microfracturing and/or debonding.
30
NonImpacted

Frequency(%)

25

Impacted

20
15
10
5

50

45

40

35

30

25

20

15

ElasticModulus(GPa)

Figure 6:

C-S-H elastic modulus of impacted and non-impacted specimens.

Frequency(%)

40
35

NonImpacted

30

Impacted

25
20
15
10
5

2.25

2.00

1.75

1.50

1.25

1.00

0.75

0.50

0.25

IndentationHardness(GPa)

Figure 7:

C-S-H indentation hardness of impacted and non-impacted


specimens.

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4 Conclusions
A novel statistical nanoindentation technique was developed that spatially
correlated the location of indents performed with an image and chemical
analyses using EDX. Using this method, the influence of high strain-rate impact
loadings on the nanomechanical properties of RPCs was determined. Significant
degradation in both the elastic modulus and hardness occurred due to impact
loadings of RPCs. Closer examination of C-S-H in particular also showed
degradation. However, a link between chemical changes in the C-S-H and
deterioration in nanomechanical properties could not be made. Based on analysis
of all indents performed on RPC specimens, it is likely that a much of the
degradation in elastic modulus and hardness observed stems from
microfracturing and debonding, which occurs due to the impact.
Future work involves additional experimental studies and quantitative data
analysis to further evaluate the possible mechanisms of degradation present in
RPCs.

Acknowledgement
Permission to publish this article was granted by Director, Geotechnical &
Structures Laboratory.

References
[1] Millard, S.G., et al., Dynamic enhancement of blast-resistant ultra high
performance fibre-reinforced concrete under flexural and shear loading.
International Journal of Impact Engineering, 2010. 37: p. 405-413.
[2] Rushing, T.S., et al., Independent effects of matrix strength and fiber
reinforcement on concrete's ballistic resistance. SAVIAC.
[3] Constantinides, G. and F.-J. Ulm, The nanogranular nature of C-S-H.
Journal of the Mechanics and Physics of Solids, 2007. 55: p. 65-90.
[4] Grady, D., Shock equation of state properties of concrete, in Proc. of
Structures under Shock and Impact IV, N. Jones et al., Editor. 1996,
Computational Mechanics Publications: Southampton, UK. p. 405-414.
[5] Velez, K., et al., Determination by nanoindentation of elastic modulus and
hardness of pure constituents of Portland cement clinker. Cement and
Concrete Research, 2001. 31: p. 555-561.
[6] Hughes, J.J. and P. Trtik, Micro-mechanical properties of cement paste
measured by depth-sensing nanoindentation: a preliminary correlation of
physical properties with phase type. Materials Characterization, 2004. 53:
p. 223-231.
[7] Ulm, F.-J., et al., Statistical indentation techniques for hydrated
nanocomposites: concrete, bone, and shale. Journal of the American
Ceramic Society, 2007. 90(9): p. 2677-2692.

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298 Materials Characterisation V


[8] DeJong, M.J. and F.-J. Ulm, The nanogranular behavior of C-S-H at
elevated temperatures (up to 700 oC). Cement and Concrete Research,
2007. 37(1): p. 1-12.
[9] Constantinides, G. and F.-J. Ulm, The effect of two types of C-S-H on the
elasticity of cement-based materials: Results from nanoindentation and
micromechanical modeling. Cement and Concrete Research, 2004. 34:
p. 67-80.
[10] Sorelli, L., et al., The nano-mechanical signature of ultra high performance
concrete by statistical nanoindentation techniques. Cement and Concrete
Research, 2008. 38(12): p. 1447-1456.
[11] MIL-STD-662F, V50 ballistic test for armor. 1997.
[12] liver, W.C. and G.M. Pharr, Measurement of hardness and elastic modulus
by instrumented indentation: Advances in understanding and refinements to
methodology. Journal of Materials Research, 2004. 19(1): p. 3-20.
[13] Chen, J.J., et al., A coupled nanoindentation/SEM-EDS study on low
water/cement ratio Portland cement paste: evidence for C-S-H/Ca(OH)2
nanocomposites. Journal of the American Ceramic Society, 2010. 93(5):
p. 1484-1493.
[14] Davydov, D., M. Jirasek, and L. Kopecky, Critical aspects of nanoindentation technique in application to hardened cement paste. Cement and
Concrete Research, 2010.
[15] Trtik, P., B. Munch, and P. Lura, A critical examination of statistical
nanoindentation on model materials and hardened cement pastes based on
virtual experiments. Cement & Concrete Composites, 2009. 31: p. 705-714.
[16] Mehta, P.K. and P.J.M. Monteiro, Concrete: Microstructure, Properties,
and Materials. 2006: McGraw-Hill Companies Ltd.

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299

Dynamic strength of concrete under


multiaxial compressive loading
Y. P. Song1 & H. L. Wang2
1

State Key Laboratory Of Coastal and Offshore Engineering,


Dalian University of Technology, China
2
Civil and Architectural Engineering College, Dalian University, China

Abstract
The dynamic characteristics of concrete are important for structures subjected to
earthquake actions. Now there is much experimental data about this, and most
are uniaxial test data. In large concrete structures, such as concrete dams,
concrete reactive power, the stress states usually are in multiaxial states;
therefore the main objective of this paper is to study the multiaxial compressive
characteristics of concrete subjected to high strain rates under multiaxial
compressive loading. Cubic specimens (100mm by side) are subjected to quasistatic and dynamic proportional biaxial and triaxial compression tests. The strain
rates used are 10-5/s , 10-4/s, 10-3/s, 10-2/s. The stress ratios are for the biaxial
compression 1:0.1, 1:0.25, 1:0.5, 1:0.75,1:1; for the triaxial compression the
applied constant confining pressures are 4MPa, 8MPa, 12MPA, 16MPa. The
tests are carried out on a concrete triaxial dynamic test system designed by the
authors. The strength characteristics of the specimens at different strain rates and
stress ratios are given. The experiment results indicate that the dynamic strength
of concrete under multiaxial compressive stress states is higher than that under
the uniaxial compressive stress state. Based on the test data, the failure criterion
is established on the octahedral stress space. Its characteristic is that the effect of
the similar angle on the dynamic strength is considered to reflect the changes of
the dynamic strength between the tensile and compressive meridians.
Keywords: dynamic strength, strain rate, biaxial stress state, triaxial stress state.

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300 Materials Characterisation V

1 Introduction
Dynamic loading on concrete structures arising from natural hazards such as
tornadoes, earthquakes and ocean waves is of great practical significance. Under
such dynamic conditions, the loading-rate dependence of material response
causes the material behaviour to be significantly different from what is observed
under quasi-static conditions. Hence a thorough knowledge of material
constitutive relationships and failure criterion, which cover a wide range of strain
rates, is very important for the design of structures subjected to all types of
loading likely to be encountered during the design lifetime.
Bischoff and Perry [1] reviewed and analyzed the response of concrete under
dynamic loads and discussed factors that influence the dynamic compressive
behaviour of concrete, such as concrete quality, aggregate type, age, curing, and
moisture conditions. Malvar and Ross [2] reviewed the existing data describing
the effects of strain rate on the compressive strength of concrete and compared
the dynamic increase factor (DIF) formulation recommended by the European
CEB Model Code [3]. However; extremely rare dynamic experiments in
multiaxial stress states are available among the current documents. For material
in multiaxial stress states, cases with biaxial compressive or triaxial compressive
loading with the other side keeps constant confining pressure are the two typical
loading patterns, which is of great significance for studying the behaviour under
arbitrary multiaxial stress states. To improve understanding of the mechanical
behaviour of concrete, experiments on the dynamic behaviour of concrete under
biaxial and triaxial dynamic compression stress states were conducted in this
research corresponding to the range of strain rates and stress states encountered
in engineering practice.

2 Experimental program
2.1 Preparation of specimens
Plain concrete cubes with a size of 100100 100 mm were subjected to biaxial
or triaxial dynamic compressive loads. Commercially available Portland cement
was used. Crushed natural stones were used as coarse aggregate with maximum
particle size of 20 mm. River sand was used as the fine aggregates. The concrete
mixture proportions by weight are water: cement: fine aggregate: coarse
aggregate =1.00:1.02:4.38:5.35. All specimens required for the aforementioned
tests were cast on the same day for each mix and covered with a plastic sheet to
prevent moisture loss. They were demoulded after 1 day and cured in the fog
room at a relative humidity of 95% and temperature of 272C till the age of 7
days. The 28-day compressive strength of concrete obtained by testing standard
cube specimens (150mm150mm150mm) is 20 MPa. Then, the specimens are
dried in air for 8 weeks before testing.

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2.2 Testing of specimens


Dynamic tests were conducted on the servohydraulic multiaxial testing system
designed and built at Dalian University of Technology, Dalian, China. The
experimental apparatus is detailed in Figure 1 with a test setup in one loading
direction illustrated in Figure 2.

Figure 1:

Figure 2:

Setup of concrete test.

Illustration of testing system in one loading direction.

The testing system allowed free and independent motion in three directions.
Along each direction, a pair of pressure levers loaded a test specimen through
two platens located on both sides of the specimen. A spherical hinge was
installed between a lever and a platen on the same side of the specimen to ensure
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302 Materials Characterisation V


that the load was exerted exactly along the load axis. The two pressure levers
were connected with a load transducer and an oil cylinder, respectively. The
nominal capacity of the testing system was 2000 kN in each direction. The servo
valve can respond to a command signal at a frequency of up to 10 Hz. Each
specimen was instrumented with six linear variable differential transformers
(LVDTs), two in each loading direction. Each LVDT had a stroke of 7 mm; it
was attached to the two platens that were connected in series with the two
opposite faces of a cubic specimen. The measured load and deformation were
transmitted to the data acquisition and the processing unit of a computer through
a specially allocated amplifier. They were then converted to stress and strain,
respectively, using the undeformed area and length of the specimen.
The selected loading paths consisted of uniaxial compression, biaxial
proportional loading compression and triaxial compression with two constant
lateral compressions. The strain rate varied from 10-5/s to 10-2/s. For biaxial
proportional compressive loading, the stress ratios of lateral pressure to the axial
load are 0:10.25:10.5:10.75:11:1. For triaxial compression with
constant lateral pressure, the constant pressure is 0, 4, 8, 12, or 16 MPa
respectively. To prevent lateral restraint of the loaded specimen, all the loaded
surfaces are polished and equipped with three layers of plastic sheet with grease
of MoS2 to reduce the surface friction to a minimum.

3 Experimental results and discussion


Table 1 and Table 2 provide the dynamic strengths under biaxial and triaxial
compression stress states. They represent the average value of each group of at
least four specimens. Note that compressive stresses in all directions are positive
in this paper.
Table 1:
Strain
rate:/s
10-5
10-4
10-3
10-2

0
9.84
10.63
11.38
12.32

Strengths at different stress ratios(2:1)


0.25
0.5
0.75
14.86
16.13
16.39
15.48
16.68
16.75
16.17
17.36
17.54
17.15
18.24
18.66
Table 2:

Strain
rate:/s
10-5
10-4
10-3

0
9.84
10.63
11.38

Biaxial test results.

4
30.05
32.11
33.70

1
14.00
15.32
16.66
18.01

Triaxial test results.


Confinement l /MPa
8
12
46.27
61.21
48.08
61.42
49.39
61.16

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16
72.14
75.34
74.08

Materials Characterisation V

303

3.1 Strength characteristics under biaxial compression


The ultimate strength of concrete in biaxial compression state is higher than the
uniaxial strength at any strain rate owing to the effect of lateral confinement. At
a specified strain rate, the strength increment depends on the biaxial stress ratio.
The maximum biaxial strength occurs at a stress ratio between 0.5 and 0.75 for
any strain rate investigated in the present study.
With the increasing strain rate, the ultimate strength at any stress ratio tends
to increase. However, the increment at different stress combinations is not
identical.
Based on the research cited above, it can be concluded that the strength
enhancement of concrete in biaxial stress states is attributed to both the strain
rate and the lateral confining pressure. A simple expression for the evaluation of
dynamic strength of concrete in biaxial stress state is suggested:
f bd
P3
P4
. .
P1 P2 lg s

2
2
fus

1 1

(1)

where s is the quasi-static strain rate, its value being selected as 10-5/s in this
.
paper; is the current strain rate; fus is the uniaxial compressive strength of
concrete at quasi-static loading; fbd is the dynamic strength of concrete in biaxial
stress state; =2/1 is the stress ratio; P1, P2, P3 and P4 represent the parameters
associated with material properties. By fitting to the test, data, P1, P2, P3 and P4
are determined as 0.446, 0.0875, 1.43 and 6.42 respectively. The multiple
correlation coefficient being 0.9580, and the mean error being 0.4122 MPa. The
suggested relationship in eqn (1) is depicted in Figure 3 and the test results are
also shown for comparison. Fairly good agreement is achieved.
.

Figure 3:

Biaxial strength envelop under biaxial stress obtained from the


proposed criterion (c&c region).

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304 Materials Characterisation V


3.2 Strength characteristics under triaxial compression
In general, the strength enhancement of concrete in triaxial stress states is also
attributed to both the strain rate and the lateral confining pressure. Newman [4]
recommended a nonlinear relation between the ultimate strength and confining
pressure. To take into account the effect of strain rates, Newmans equation is
modified to
2

f
A( ) lat B() lat 1 c 0
f
f
f
us
us
us

(2)

where A( ) a b lg( ) , B ( ) c d lg( ) ; fus is the uniaxial compressive


strength of concrete at quasi-static loading rate ; lat is confining pressure; the
material constants a, b, c, and d are determined in this study to be 2.22, 1.54,
23.7, and 1.19, respectively. Figure 4 shows the ultimate strengths at various
strain rates as a function of the confining pressure. For comparison, eqn (2) was
plotted in Figure 4 as well. It can be seen from Figure 4 that eqn (2) is in
excellent agreement with the test data. It should be noted that the values
predicted by the formula only make sense when confining pressure is smaller
than the uniaxial static strength of concrete.

(a)

(b)

(c)
Figure 4:

Triaxial strengths of concrete at various strain rates.

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4 United failure criteria in octahedral stress space


Based on the strength characteristic of experimental results in Table 1 and
Table 2 and theoretical analysis of the failure enveloping plane, the present paper
proposes a new failure criterion as the following:

oct
f cs



a1 b1 oct c1 oct
f cs
f cs

(3)

where oct 1 1 2 3 , oct 1 1 2 2 2 3 2 3 1 2


3

;a1,b1,c1

are parameters depending on the loading rate, which can be determined by fitting
to the test data, as listed in Table 3.
Table 3:
Strain rate/s-1
10-5
10-4
10-3
10-2

a1
0.2033
0.2865
0.3550
0.4187

Fitting results.
b1
0.9730
0.7384
0.5723
0.4708

c1
0.4816
0.2948
0.1647
0.0975

R2
0.9547
0.9497
0.9505
0.9407

A total of 236 experimental data points of concrete under dynamic biaxial


compressive loads and triaxial compressive loads, were used in the verification
of the proposed failure surface for concrete under dynamic loading, as illustrated
in Figure 5. Comparisons in Figure 5 indicate that the failure envelope in the
octahedral stress space gradually expands with the strain rate.

Figure 5:

Summary of biaxial and triaxial compressive test data and the


proposed envelopes.

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306 Materials Characterisation V

5 Conclusions
The dynamic behavior of concrete in biaxial and triaxial stress state has been
experimentally studied under linearly increasing loads of high strain rates. Based
on the extensive test data and analyses, the following conclusions can be drawn:
(1) The ultimate strength of plain concrete nonlinearly increases with its
confining pressure at all load/strain rates that were considered in this study, but
the magnitude of increment depends on the lateral stress ratio.
(2) At low confining pressure, the ultimate strength of concrete increased
with the strain rate. When the confining pressure was approximately higher than
the uniaxial static strength, the ultimate strength tended to vanish with the strain
rate.
(3) Under biaxial and triaxial stress state, the failure envelope in the
octahedral stress space gradually expands with the strain rate.
(4) The proposed united strength criterion for concrete under multiaxial
stress state reasonably reflects both the effect of strain rate and the effect of
lateral confinement. Fairly good agreement with experimental results is
achieved.

Acknowledgements
This study was supported by the National Natural Science Foundation of China
under Grants 90815026 and 51079019 at Dalian University of Technology,
Dalian, China, and Grant 50908026 at Dalian University, Dalian, China.

References
[1] Bischoff, P. H., Perry, S. H., Compressive Behavior of Concrete at High
Strain Rates. Materials and Structures, 24 (2), pp. 425-450, 1991.
[2] Malvar, L. J., Ross, C. A., Review of Strain Rate Effects for Concrete in
Tension. ACI Materials Journal, 95(6), pp. 435-439, 1998.
[3] Comit Euro-International du Bton, Model Code 90, CEB-FIP, Redwood
Books: Trowbridge, Wiltshire, UK, pp. 48-51, 1990.
[4] Newman, J. B., Concrete under Complex Stresses. Development in Concrete
Technology-1, F. D. Lydon, ed., Applied Science Pub: London, UK, pp.
151-219, 1979.

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307

Modelling and simulation of the


rutting resistance of bituminous mixes:
experimental and stochastic approaches
A. E. Ouni1,2, A. Dony2 & J. Colin2
1

Arts et Mtiers ParisTech (ENSAM), France


Ecole Spciale des Travaux Publics, du Btiment et de l'Industrie
(ESTP), Institut de recherche en constructibilit (IRC), France

Abstract
This work deals with the simulation of the rutting resistance of bituminous
binders used in road pavement. First, the experimental protocol was assessed to
simulate pavement traffic allowing the prediction of the rutting depth evolution
versus cycle number of wheel passes under isothermal conditions. Then a
probabilistic parametric approach was developed to take into account the
different parameter uncertainties related to the changes in experimental
conditions. We investigate through the stochastic approach the rutting sensitivity
of bituminous mixes under traffic load. A confidence region of a high probability
of 99% is defined to allow the prediction of the in situ rutting potential of
bituminous specimens.
Keywords: rutting, bitumen, uncertainties, stochastic.

1 Introduction
The environment protection has been and continues to be the major concern of
the road politics in industrialized countries. With the signature of the Kyoto
protocol agreement, the European Union is involved to reduce the energy
consumption and the resulting greenhouse gases emissions [1]. The warm mix
asphalt (WMA) is a promising technology which has been developed to
contribute to the protection of the environment and sustainable development
program [25]. The WMA is a mixture of mineral aggregates and bitumen
produced and placed on the road at a lower temperature comparing to the
traditional hot mix asphalt (HMA). Reductions in temperature of 20-50C have
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308 Materials Characterisation V


been recorded. As a result, significant benefits were noted through the energy
saving and the reduced emissions from burning fuels, undesirable fumes and
odors generated at the plant and paving site. Typically, the HMA is produced at
140C-180C to make the binder viscous enough to coat the aggregate and to
ensure a good workability of the asphalt during laying and compaction. In the
case of WMA, there are some techniques developed and used in European
countries to produce mix asphalt at low temperature without altering the
workability of the mixture [6].
During its service life, the road pavement experiences multiple failure modes
such as permanent deformation (rutting), fatigue and thermal cracking [7, 8]. The
rutting phenomenon occurring at high service temperature is essentially due to
the mechanical traffic load. The accumulated strains resulting from the vehicle
passes lead to a plastic deformation in pavement layer. Due to the excessive
pavement rutting, water and snow can stagnate in the ruts, for example, and lead
to vehicle hydroplaning and accidents. Accordingly, the WMA is required to
exhibit a good rutting performance once in pavement. In addition, the laboratory
measurements of rutting exhibit very often some dispersion linked to the
experimental uncertainties. It was shown by the authors in a previous work [9]
that this probabilistic aspect has to be taken into account in order to have an
accurate prediction of asphalt rutting performance through bitumen
characteristics.
In this context, the aim of this paper is to emphasize though a rutting test
carried on warm and hot bituminous mixtures the necessity to consider the
experimental uncertainties in order to quantify the random response related to the
rut. Suitable probability distributions were developed on the light of the
statistical information derived from experiments to describe the random
stochastic variable attributed to the rut.

2 Experimental program to evaluate rutting performance


2.1 Material description
This study is carried out by considering a Semi-coarse asphaltic concrete (BBSG
0/10) formulated as follow:
Table 1:

Composition of asphalt mixture.

0/2 Noubleau

2/6 Noubleau

6/10 Noubleau

33%

20%

45%

Filler calcaire
Piketty
2%

35/50
Bitumen
5%

The bituminous mixture specimens were prepared in laboratory (ESTP


France). First, hot mix asphalt (HMA) was prepared by mixing aggregates
together with bitumen at a mixing temperature of 165C. Then warm mix asphalt
(WMA) was obtained by mixing the components at 110C. During the
preparation of WMA and in order to improve the workability of the asphalt

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309

binder so that it can be sufficiently viscous to coat the aggregate, a surface active
additive was incorporated at 0.3% into the bitumen.
2.2 Laboratory compaction
To produce representative specimens for rutting test, slabs were manufactured
with the prepared bituminous mixes and afterwards compacted in moulds by a
roller compactor device (LCPC France) according to the standard
specifications (NF EN 12679-33). The apparatus (Fig. 1) provides a
pneumatically powered means of compacting slabs to reproduce in situ
compaction. The dimensions of the obtained slabs are 500 mm x 180 mm x
100 mm.

Figure 1:

Figure 2:

Slabs roller compactor.

French rutting test device.

2.3 Rutting test


There are several types of wheel tracking devices that can be used to evaluate the
rutting potential of a mixture. The three most known laboratory devices are the
Asphalt Pavement Analyser (APA), the Hamburg Wheel Tracking Device
(HWTD) and the French Public Works research Laboratory (LCPC) wheel
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310 Materials Characterisation V


tracker commonly known as the French Rutting Tester (FRT). For further
information on these devices, the reader could consult [10]. Here, the FRT is
used to evaluate the permanent deformation of the bituminous mixtures. This
device has been used in France for over 15 years to simulate the traffic load
through repetitive passes of a wheel pressurized to 0.6 0.03 MPa. The FRT
(Fig. 2) tracks across an asphalt specimen (slab) a loaded wheel of 500 N for
many thousands of cycles. The rutting test was performed conforming to the
standard specifications (NF EN 12679-22).
Accordingly, the temperature was monitored uniformly and maintained to
60C by temperature sensors inserted within the slab while local deformation is
continuously recorded by depth gauge. Here, 2 slabs of HMA and WMA
mixtures were tested simultaneously on the rutting device. After the required
number of cycles, the rut depth was measured in mm at 15 different positions on
the slab and then an average value of the rut is considered. Here, a load cycle
corresponds to an outward and return motion of the wheel. In the following, ri
denotes the local rut depth measured at the position (i) on the slab. The rut after n
cycles is expressed in percent (%) according to eqn (1):
Rut %

100

(1)

where r0i represents the initial measurements at the positions (i) located on the
slab and h its thickness.
In figure 3, we present the evolution of the rut depth in percent versus the
number of cycles for both hot and warm asphalt mixes. One can see that the 2
mixtures exhibit nearly the similar performance with a better rutting resistance of
the HMA particularly with the increasing of the cycles number. In fact, we
recorded after 30 000 cycles a rut depth of 4.23% for the HMA versus 6.53% in
the WMA case. We note that in the French specifications [8], the maximum of
rut depth shall be less than 10%. This constraint is marked by a dark continuous
line in figure 3.

Rut(%)

10

HMA
WMA

0.1
100

1000

10000

Cycles
Figure 3:

Rutting test results.

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Materials Characterisation V

311

3 Parametric probabilistic modelling of experimental


uncertainties
3.1 Stochastic approach
In this section, we will make use of the experimental uncertainties derived from
the aforementioned rut depth values measured on the top surface of the slab. The
15 local measurements ri recorded after n cycles allow the definition of average
and standard deviation values for the rut depth. In the following, we will denote
by R (in bold letters) the random variable associated to the rut in percent. In
order to describe the random uncertainties of this variable, the entropy maximum
principle (EMP) is considered for the probabilistic parametric modeling [11, 12].
In general, given a random variable X, The EMP allows the construction of
adequate and realistic probability density functions (pdf for short) of X on the
light of the given information. Accordingly, the dispersion of X is described by
the pdf pX and it is quantified by the entropy S:

S ( X ) p X ( x ) log( p X ( x )) dx

(2)

The given or available information may be the average (or mean) of the
variable, the standard deviation, the second or higher order moments, etc. The
entropy maximum principle states that the suitable probability density function
which describes the random variable distribution is obtained by maximizing the
entropy S. This leads to an optimization problem constrained by the known
information formulated as follow:

Maximize S(X), subject to:



p X ( x)dx 1
(3)

fi g i ( x) p X ( x)dx
i=1 to n,

where fi, represent the available information. For instance, if fi = mX (mean of the
random variable X), g(x) = x whereas when fi = m2 (second order moment), g(x)
= x.
This optimization problem can be solved by minimizing a Lagrangian
function H which includes (1+n) Lagrange multipliers (0, i, i =1 to n)
associated to the (1+n) constraints. The function H is given by:

,,

exp

where [a, b] denotes the support of the random variable and


function defined as:

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(4)
,

an indicator

312 Materials Characterisation V

1ifx a, b
0ifnot

(5)

Once i are found, the probability distribution of the random variable is


known and it is given by:

exp

(6)

3.2 Results
To illustrate this methodology, we focus on the rutting results obtained at 30 000
cycles. The average and standard deviation values of the rut for Hot and warm
bituminous mixtures are recapitulated in table 2.
Table 2:

Statistical data of the rut in percent.


Average_rut

Standard deviation_rut

HMA

4.23

1.62

WMA

6.53

0.74

In our case, given the average and the STD values and assuming that the
random variable associated to the rut depth shall not take nor negative neither
infinite value, the minimization of Eq. (x) leads to a Gaussian distribution:
pRut ( r ) exp( 0 1r 2r 2 )

(7)

Figure 4 presents the probabilistic distributions as well as numerous random


trials (1000 in total) of the rut according to the probability density function for
both hot and warm asphalt mixes. The red continuous line corresponds to the
average value of the rut in percent. Analogically, we can follow the same
methodology to determine the rut pdf after 100, 300, 1000...cycles. Then, after a
given number of cycles, we carry out some random realizations according to the
pdf. This will be useful to define a confidence region including the probabilistic
responses of the rut.
In figure 5, we show the random variation of the rut value versus the number
of cycles for HMA and WMA cases. As can be seen, the mean (or deterministic)
model using the average values of the rut lies in the middle of the confidence
region. In addition, one can note that even though the confidence regions of the 2
mixtures are very close at the beginning of the test which seems to be positive
for warm asphalt rutting performance, the discrepancy increases for higher
number of cycles where the intervals become more spaced.

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Materials Characterisation V

(a)
Figure 4:

313

(b)

Probabilistic density functions of the rut and random realizations,


(a) HMA, (b) WMA.

Figure 5:

Confidence regions for rut.

4 Conclusion
A series of experimental tests were performed in this paper to compare the
rutting performance of HMA and WMA obtained by the incorporation of surface
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314 Materials Characterisation V


active additive. The rutting test FRT shows that both asphalt mixes exhibit
comparable rutting performance after 30 000 loaded cycles. This finding added
to the environmental advantageous outlines the beneficial use of warm mix
asphalt technology in road pavement. The stochastic approach was developed on
the light of the available statistical information derived from the experimental
uncertainties linked to the rut measurements. Accordingly, confidence regions
were defined to estimate the probabilistic rut depth response with respect to the
adequate probability density function. Discrepancies in confidence intervals are
noticed between the 2 mixtures especially for a high number of wheel passes.
In the future, it would be interesting to investigate the modification of
rheological and chemical properties of the bituminous binders recovered from
the mixtures. This study could improve our knowledge and understanding of the
bitumen ageing phenomenon.

References
[1] International Technology Scanning Program, Warm-Mix Asphalt:
European Practice, 2008.
[2] Brosseaud Y., Ecologiques, scuritaires, confortables, les enrobs de
demain se feront autrement : Prsentation des enrobes tides, 2006.
[3] Collectif. Un sujet chaud, les enrobs basses calories. Bitume info. N12,
pp. 12-15, 2006.
[4] Brosseaud Y., Warm asphalt-Overview in France. LCPC, France,
Prsentation to WMA scan team, 2007.
[5] Brosseaud Y. & Saint Jacques M, Warm Asphalt Mixes: Overview of This
New Technology in France, Second European Road. Transport Research
Arena Europe, Ljubljana, Slovnie, 21-24, 2008.
[6] Harder, G. et al (2008). Energy and environmental gains of warm and halfwarm asphalt mix: quantitative approach. In: Transportation Research
Board, Washington D.C., 2008.
[7] Warm mix asphalt technologies and research, Government engineering,
July-August, 2007.
[8] Perraton D., Di Benedetto H., Sauzat C. et al., Rutting of bituminous
mixtures: wheel tracking tests campaign analysis. Materials and structures,
Online First, 2010.
[9] Eddhahak Ouni A., Dony A. & Colin J., Assessment of a probabilistic
parametric rheological model to predict the rutting resistance of bitumen,
ASMDO 2010.
[10] Cooley Jr., Allen L., Prithvi S. Kandhal, & M. Shane Buchanan. Loaded
Wheel testers in the United States: State of the Practice. Transportation
Research Board E-Circular number E-C016, 2000.
[11] Shannon, C.E., A Mathematical Theory of Communication, Bell System
Technical Journal 27, pp. 379423 & 623656, 1948.
[12] Jaynes, E.T., Information theory and statistical mechanics, Physical
Review 106, pp. 620-630, 1957.

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Materials Characterisation V

315

Laboratory tests on the cleanliness of


soil materials used as subgrades in
pavement structures
A. Athanasopoulou & G. Kollaros
Democritus University of Thrace, Greece

Abstract
In order to ascertain the presence of very fine material passing the No. 200 sieve,
cleanliness tests are performed in the laboratory. The most important of these
tests refer to the determination of the quantity of fines, of the sand equivalent
value, of the plasticity index, as well as the methylene blue value of the material
tested. Performing the sand equivalent test the percentage of very fine dust in
claylike form can be established. Materials with very low sand equivalent are
characterized as impure and the possibility of the existence of clay size grains
in them is very high. In such cases it is necessary to perform a test in order to
determine the plasticity of the soil material. The determination of the plasticity
index of natural soils specifies their suitability as subgrade layers in pavement
structures. Soils having a sand equivalent value lower than 10% will develop
excessive swell with a simultaneous decrease in their bearing capacity when a
pavement is built on them. The quantity of methylene blue absorbed by clay
components of a soil mass is proportional to the specific area of the clay
minerals. The methylene blue test supplements the sand equivalent and Atterberg
limits tests, since with these the existence of clay-size grains is determined, but
not the existence of active clay minerals as well. A number of soil samples have
been examined in the laboratory, involving the procedures of cleanliness tests.
The quantity of fine grained material was determined and their activity was
accessed. The magnitudes were correlated in order to check the suitability of
soils as a pavement foundation. Empirical relationships have been established
which connect the attributes characterizing the cleanliness of soil materials.
These relationships compare very well with most of the findings published
worldwide.
Keywords: swelling soils, methylene blue test, sand equivalent, cleanliness.
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316 Materials Characterisation V

1 Introduction
In most pavement structure techniques, suitability is one of the essential
characteristics of soil materials. The term "suitability" characterizes the absence
of undesirable elements. These elements are soluble salts, iron hydroxides,
organic matter, as well as clays. They can present sickliness because of their
fineness, their physicochemical activity or because of their effect in the binding
materials. In view of their frequency of appearance in alluvial deposits and rocks,
their hydrophilic nature, and of their affinity and plasticity properties, clays are
the most harmful.
Swelling soils often cause serious damages in pavement structures, while, on
the other hand, they cannot be used as embankment material in roads. The
swelling potential of soils is mainly affected by their clayey fraction (Kollaros
and Athanasopoulou [1]). In order to ascertain the existence of very thin material
passing the No. 200 sieve cleanliness tests are performed. The more important
tests are consisted in the determination of the quantity of fines, of the plasticity
index, the equivalent sand and the methylene blue value.
The quantity of material passing the 0,075 mm sieve (#No. 200), expressed as
a percentage of the total material, is determined by the sieve analysis test, either
through the dry or, more usually, through the wet process, according to
AASHTO T88 or ASTM D422 standards.
The plasticity index, which is defined as the difference in contained moisture
between the liquid and plasticity limits: PI=LL-PL, it is a value that helps to
recognize soil characteristics and to properly classify them. The plasticity index
determines the appropriateness of soils to be used as subgrades in roadway
foundations. Soils having a high PI value, such as clayey, silty and some sandsilt soils, are inadequate for the foundation of pavements. In Table 1 the degree
of plasticity is given in terms of PI and of soil characteristics in a dry condition,
for the corresponding scale of the PI values.
The plasticity index is useful for materials containing high percentages of silt
and clay, while in the region not covered by the PI use is made of the sand
Table 1:
PI
>35
16-35
7-15
4-6
0-3

Soil
Highly
Plastic
Plastic
Medium
plasticity
Slightly
plastic
Non Plastic

Soil characterization as a function of PI.


Soil characteristics in dry condition
High cohesion value, manual smashing of lumps is
impossible
Medium to high cohesion, difficulty in smashing lumps
manually
Low to medium cohesion, lumps are smashed by exerting
a low pressure to them
Low cohesion, easy manual smashing of lumps
Very little cohesion or complete absence of cohesion,
lumps are decomposed by a simple touch

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Materials Characterisation V

317

equivalent value. The sand equivalent, SE, test arose in view of the need for a
quick quality indication of paving materials. This test was devised by Hveem in
1953, it was put in use in 1956 and it has been adopted for laboratorial use since
1966.
More specifically, with the sand equivalent test the proportion of very fine
dust of claylike form is determined. For a SE<20 value, the plasticity index
should be determined. In the region of higher SE values, the plasticity index is
not determined (Non Plastic) and therefore it cannot replace the sand equivalent.
On the basis of comparisons of sand equivalent values to the results of other
tests it has been found that most of the soils presenting high swell potential when
saturated with water, is possible to be recognized by the SE value. Soils on top of
which a pavement is to be constructed develop excess swell, with a simultaneous
decrease of their bearing capacity in saturated conditions, provided that the SE
value is lower than 10%. The different fine grained materials could be classified
in three groups, as shown in Table 2, depending on their sand equivalent value.
Table 2:

Classification of fine-grained materials as a function of SE.

Sand Equivalent
High Values
Medium Values
Low Values

Fine-grained materials
Clean non-cohesive sands
Sands blended with some quantities of silt and clay
Clays and silt-clayey mixtures

In order to measure the unsoundness of sands, the Laboratoire Centrale des


Ponts et Chausses, in France, examined two different methods. According to the
first procedure, the process of the sand equivalent test was modified, to become
more compatible for the recognition of sands rich in fine-grained material. Thus,
in the AFNOR NF P 18-597 standard, "Proprets des Sables", the following
modifications were made:
Test sampling using the 2 mm sieve, instead of the 4.75 mm sieve (#No. 4).
The percentage of elements finer than 0.08 mm is kept to a constant value
equal to 10%.
With the second procedure, the test is supplemented with a different measure,
namely the capacity of the clayey components to absorb some basic dye such as
the methylene blue.
The methylene blue test has basically been developed in an effort to
determine the clay content of a soil. In 1980 the test was adopted for aggregates
and in 1984 the method of methylene blue with agitation was proposed by Tran
and Millon-Devigne [2] in order to increase the precision of the test and to make
it capable of measuring properties on least clayey samples.
The test is based on a successive import of increasing quantities of methylene
blue solution in a suspension of the material to be examined, until the claylike
particles are saturated with dye. Saturation has been achieved when a spot of soil
coloured by the retained dye of soil is shaped, surrounded from a colourless area of
humidity ("spot" control) on a filter paper. The control is positive, if in this zone
an excess of dye appears in the form of light blue coloration, which surrounds
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318 Materials Characterisation V


radially the central dark blue trace of the drop. The spot test is repeated after two
minutes. If the solution continues to demonstrate an excess of dye, the "final
point" has been reached. It must be noted that an experienced person can reach
faster the final point, omitting some initial doses of methylene solution.
The methylene blue test supplements the sand equivalent and Atterberg limits
tests, since they determine the existence of particles with claylike dimensions,
but not the presence of active clay minerals.

2 Laboratory testing of soil samples


Soil samples were collected from twenty six sites located in the Evros prefecture.
The criterion used was their proximity to road works and the probability that
they could create constructional problems due to large percentages of clay. The
properties of these materials ranged in the limits presented in Table 3.
Table 3:

Properties of the soils tested.

Soil Property
Clay content (material < 2) (%)
Percentage passing the No. 200 sieve (%)
Liquid Limit (%)
Plasticity Limit (%)
Plasticity Index (%)
Linear shrinkage (%)
Volume of dye, Vd (cm3)
Sand equivalent, SE
Skempton Activity [PI/(%material<2)]

Mean Value
41.42
74.65
52.73
22.24
29.73
12.93
20.35
14.46
0.71

Range of values
954
29.2390.13
2976
1729
1747
10.015.7
627.5
533
0.581.00

The swelling potential of soils is influenced by the percentage of the clay


fraction they contain as well as by the composition of this fraction. The grain
size analysis of soil samples revealed that most of them had high content of clay
(material with grain diameter smaller than 2 microns).
When the grain size analysis was performed using sieves with standard
openings, the presence of high percentages of very fine material passing the No.
200 sieve has been recorded. Only two samples had particles with a diameter
smaller than 0,075 mm in a percentage smaller than 50%.
The Atterberg limits tests resulted in high values for the plasticity index. The
PI values were above 15 for all soil samples, reaching even a value of 47,
suggesting that the soils were very plastic and in a dry condition it was very
difficult to smash any formed lump. The determination of PI was not possible for
one of the samples. Soils having such PI values are inadequate for the foundation
of pavements.
The swelling degree could be calculated with the Holtz-Gibbs classification
method, which is based on the plasticity index and the colloid content of the
samples. Twenty two samples are characterized by a very high or high swelling
degree, while only 4 showed medium and low swelling degree. Generally, the
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Materials Characterisation V

319

clays in the region fall in group A-7 according to the AASHTO classification
method. This group involves soil materials poor or unsuitable to be used as
foundation.

3 Correlation of attributes used for soil characterization


With the completion of laboratory testing, a statistical correlation of attributes
used for the characterization of soil materials was attempted. Special attention
has been focused mainly on those values resulting from the test which specifies
the clayey ingredients using the methylene blue and the sand equivalent
procedures. The selection of these properties can be easily justified taking into
account the high percentages of fine grained material in the samples and the
relatively high swelling degrees that are expected in the field, constituting a
source of dangers for the integrity and longevity of pavement structures.
The sand equivalent values resulted as the mean of three repetitions of the
standard process for each sample. In the methylene blue test the volume of dye,
Vd was measured.
50

Plasticity Index, PI (%)

40

30

20

10
20

30

40

50

60

Material finer than 2 (%)

Figure 1:

Plasticity index variation with material finer than 2.

The distribution of plasticity index values, as estimated by the percentage of


material finer than 2 as well as from the results of the methylene blue test is given
in figures 1 and 2, respectively. The linear correlation of these attributes with the
plasticity index is particularly good, since the coefficients of determination in these
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320 Materials Characterisation V


cases are R2=0,73 and R2=0,58. Equations (1) and (2) interrelate the results
obtained for the plasticity index and the other two properties.
PI=0,606 (%material<2)+5.02

(1)

PI=1,201Vd+5.79

(2)

In particular, a high degree of correlation has been obtained for the methylene
blue value and the percentage of claylike fraction in the samples tested. The
linear regression eqn. (3) connecting these attributes gave a coefficient of
determination, R2, equal to 0,82.
%material< 2=2.019Vd+0.34

(3)

In figure 3 the variation of the percentage of material with particle diameter


smaller than 2 against the Volume of dye calculated by the methylene blue
method is presented.
A similarly good linear correlation appeared between the volume of dye of
the samples and the percentage of material passing the sieve No. 200, as shown
in figure 4. The coefficient of determination, R2, for the relation connecting the
two attributes in eqn. (4) has been found equal to 0,69.
%material< No. 200=2.409 Vd+25.63

(4)

50

Plasticity Index, PI (%)

40

30

20

10
10

12

14

16

18

20

22

24

26

28

Vd (cm )

Figure 2:

Plasticity index variation with volume of dye, Vd.

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30

Materials Characterisation V

321

Material finer than 2 (%)

60

40

20

0
5

10

15

20

25

30

Vd (cm )

Figure 3:

Variation of the percentage of material <2 as a function of the Vd.

Material passing # No. 200 (%)

100

80

60

40

20
5

10

15

20

25

30

Vd (cm )

Figure 4:

Variation of material passing # No. 200 as a function of the


Volume of dye, Vd.

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322 Materials Characterisation V

Material passing # No. 200 (%)

100

80

60

40

20
0

10

15

20

25

30

35

Sand Equivalent, SE

Figure 5:

Variation of the percent passing # No. 200 as a function of the sand


equivalent value.

In eqn. (5) the sand equivalent value, SE, is the independent variable and the
percentage of material passing the sieve No. 200 is the dependent variable. This
equation yielded a coefficient of determination, R2= 0,66.
%material< No. 200=1.994 SE+103.48

(5)

The sand equivalent values have been related to the respective values
obtained by the testing of the samples using the methylene blue test. The
equation of the curve that fits to the data in figure 6 has a coefficient of
determination, R2= 0,43 and is depicted in eqn. (6).
Vd=-0,587 SE+28.98

(6)

The negative gradient of the regression lines in figures 5 and 6 means that an
increase of the sand equivalent entails a reduction in the respective values of both
the fine-grained material and the quantity of dye absorbed by the clay particles.
Empirical relations similar with those resulted from the statistical processing
of the laboratorial results, have been reported in the international bibliography.
Many research efforts have been devoted to the correlation of the Atterberg
limits with the attributes tested and with the cation exchange capacity, CEC.
High level of correlation (r=0,80) has been obtained between the plasticity index
and the CEC (Taylor [3]). Also, a coefficient R2=0,56 was found for the relation
of the Skempton activity (PI/% of material<2) with the cation exchange
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Materials Characterisation V

323

30

Vd (cm3)

26

22

18

14

10
0

10

15

20

25

30

Sand Equivalent, SE

Figure 6:

Variation of Vd as a function of the sand equivalent value.

capacity (Sweere and Galjaard [4]). The plasticity index of 70 Illinois clay
samples (Odell et al. [5]) was fairly correlated with the content of material<2
through the eqn. (7):
PI=0,568 (%material<2)+1.09

(7)

A very good correlation between the apparent surface area calculated by the
methylene blue test and the percentage of particles having a diameter smaller
than 1 has been found by Xeidakis [6]. In this research 8 clayey minerals had
been tested and a correlation coefficient r=0,946 was found. A relatively weaker
correlation (r=0,65) has been reported for 19 British soils (Farrar and Coleman
[7]) which contained some montmorillonite.
Nikolaides et al. [8] published the results of SE and MB values obtained at 16
samples from Greek quarries. They found that there is no correlation between
MB and SE values.
The results of a series of tests performed on aggregates from production sites
and 45 mixtures prepared in the laboratory to clarify the effect of potentially
harmful fines on the MB and SE values are described by Petkovek et al. [9].
Particular attention is paid to the prediction of approximate limits for SE and MB
values, taking into account the specific geological conditions of the aggregate
sources and past experience using the same aggregates.

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324 Materials Characterisation V

4 Conclusions
Swelling clay soils are abandoned in the region of Thrace, Northern Greece,
presenting many risks for the construction of pavements. In a new classification
system, it is possible for soils with homogeneous technical attributes to be
distinguished in categories, which they will be based on the activity of the clayey
phase -more specifically on the total specific area, that is, on the methylene blue
value- in combination with their grain-size gradation.
The methylene blue test has been found to be an easy and very repeatable test
method. Because of their simplicity, the suitability controls which are supported
by the laboratorial tests, can be also conveyed in field testing.
The correlation of values of attributes obtained from the tests in methylene
blue with the respective values of the plasticity index, the soil gradation (clay
fraction, percent of material passing the No. 200 sieve) and with the sand
equivalent showed that linearity exists in these relations and that the correlation
coefficients were particularly high. For the relations to merit general application,
they should be confirmed with the repetition of experimental processes in many
more samples from the region of Thrace.

References
[1] Kollaros, G. & Athanasopoulou, A., The character and identification of
swelling soils in road construction projects, Proc. International Symposium
on Engineering Geology and the Environment IAEG, eds. Marinos, Koukis,
Tsiambaos & Stournaras Balkema: Athens, pp. 187-192, 1997.
[2] Tran, N.L. & Millon-Devigne, P., L'essai au bleu de mthylne en
turbidimtrique, Bulletin de lAssociation Internationale de Gologie de
lIngnieur, 29(1), pp. 453-456, 1984.
[3] Taylor, R.K., Cation exchange in clays and mudrocks by methylene blue. J.
Chem. Tech. Viotechnol., 35A, pp. 195-207, 1985.
[4] Sweere, G.T.H. & Galjaard, P.J., The methylene blue test as a rapid means
of estimating the cation exchange capacity of soils. International Symposium
of Geotechnical Aspects of Mass and Material Transportation, Bangkok, pp.
47-52, 1984.
[5] Odell, R.T., Thornburn, T.H. & McKenzy, L., Relationships of Atterberg
limits to some other properties of Illinois Soils. Proceedings of the Soil
Science Society of America, 24(5), pp. 297-300, 1960.
[6] Xeidakis, G.S., Assessment of the engineering and other properties of
expansive soils by various methods. Ph.D. Thesis, Dept. of Civil
Engineering, University of Leeds, England, 407 p., 1979.
[7] Farrar, D.M. & Coleman, J.D., The correlation of surface area with other
properties of 19 British clay soils. Journal of Soil Science, 18(1), pp. 118124, 1967.

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Materials Characterisation V

325

[8] Nikolaides, A., Manthos, E. & Sarafidou, M., Sand equivalent and methylene
blue value of aggregates for highway engineering. Foundations of civil and
environmental engineering 10, Publishing House of Poznan University of
Technology, Poznan, pp 111-121, 2007.
[9] Petkovek, A., Maek, M., Pavi, P. & Bohar, F., Fines characterization
through the methylene blue and sand equivalent test: comparison with other
experimental techniques and application of criteria to the aggregate quality
assessment, Bull Eng Geol Environ 69, pp. 561574, 2010.

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Materials Characterisation V

327

Use of additives to improve the


engineering properties of swelling soils in
Thrace, Northern Greece
A. Athanasopoulou & G. Kollaros
Democritus University of Thrace, Greece

Abstract
Highway construction engineers often face the need for more stable, durable and,
at the same time, more economic road structures. This is nowadays true because
of increased traffic volumes and heavier loads on the roadways. As a
consequence, enhanced pavement structures and improved subgrades is a
necessity. The international highway New Egnatia crosses areas in Thrace,
Northern Greece with abundant clayey soils having poor technical properties.
The treatment of physical soils with some substances could bring up new
materials, which would operate better under the traffic and environmental
conditions. This has led to the decision to investigate the possibilities of
improving the existing soil materials using chemical additives. Soil samples were
collected from the abovementioned area and mixed with lime and fly ash, in
various proportions. The modification of the soil properties with special
emphasis on their strength has been examined in the laboratory after different
curing periods.
The experimental results have shown that the unconfined compressive
strength increased as a function of both the percentage of additive in the mixture
and the time of curing. The improvement depended upon the soil mineralogy and
the kind and quantity of exchangeable cations. This holds true when the
influence of the kind and quantity of the additive is taken into account. The
effects of lime on the swelling clayey soils tested were more beneficial than
those of fly ash.
The soils after their treatment could be used as a subgrade or even as a
subbase layer in roadway pavements.
Keywords: stabilization, lime, fly ash, engineering properties, unconfined
compressive strength, optimum moisture.
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328 Materials Characterisation V

1 Introduction
The continuous growth of the traffic volume and of vehicle's size, has made
obvious the need for more stable, durable and, at the same time, more economic
road structures. Consequently, a requirement exists for improved properties of
the pavement structure as well as of the physical subgrade. The treatment of
physical soils and base materials with some substances could bring up new
materials, which would operate better under the traffic and environmental
conditions. In this procedure, called soil stabilization, such substances as
Portland cement, bituminous materials, lime, fly ash or alkali salts could be used.
It has been recognized by numerous investigators (Bell [1], Zhang and Cao
[2]) that the addition of lime and/or fly ash to soil materials may cause various
beneficial changes to the engineering properties of fine-grained soils, such as the
reduction of plasticity, the reduction of shrinkage-swelling potential and the
improvement of strength characteristics.
Roadways have a high potential for large volume use of the fly ash stabilized
soils. Arora and Aydilek [3] investigated the use of Class F fly ash amended soilcement or soil-lime as base layers in highways. Unconfined compression, CBR,
and resilient modulus tests were conducted. Required base thicknesses were
calculated using the strength parameters. The strength of a mixture is highly
dependent on the curing period, compactive energy, cement content, and water
content at compaction. Lime treatment didnt provide sufficient strength for
designing the mixtures as highway bases.
The strength of soil-lime-fly ash mixtures could be estimated by various
methods such as unconfined compression, CBR, the Hveem stabilometer and
triaxial tests. The most commonly used method is the unconfined compression
test, not necessarily being the most appropriate for all purposes. The strength of
soil-lime or soil-fly ash mixtures depends on many variables such as the soil
type, the lime and fly ash content, the additive type, the time and method of
curing (temperature and humidity), the water content, the unit weight and the
time interval between mixing and compaction (oka [4]).
The addition of lime, fly ash, and lime/fly ash to three clayey soils led to a
reduction of the plasticity index and contributed to an increase in the optimum
moisture content and a decrease in the maximum dry density (Hesham [5]). The
optimum lime content ranged from 3 to 5%, while the optimum fly ash content
between 16 and 35%. The optimum lime/fly ash content for the three soils was
(2.5%L+8%FA), (2%L+12%FA) and (3%L+20%FA). The UCS, Esecant, CBR,
and the Velocity of ultrasonic p-waves, Vp, values increased slightly with an
increment of the dry density of the untreated compacted soils (due to the
compaction process) and strongly due to the addition of the chemical stabilizing
agents (lime, fly ash, and lime/fly ash) whereas the formed cementitious
compounds (as a result of the chemical reactions between the silica and the
alumina and the additives) joined the soil particles.
Basic studies on pozzolanes and on the pozzolanic properties of fly ash have
been carried out by Adu-Gyamfi [6] and Brooks [7]. Considering the nature of
the lime used in the mixtures, many investigators such as Ingles and Metcalf [8],
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Materials Characterisation V

329

have shown that calcarious limes gave higher strength results than those given by
dolomitic limes.
In Greece, many roads have been built using stabilization techniques for the
subbase materials. The behaviour of these roads has been judged as fairly
satisfactory. The scope in some of these trials was the use of large quantities of
fly ash per surface unit, in order to take advantage of the surplus of this material.
However, the cost of transporting the material from places of its production or
deposition to the areas of the projects under consideration, which are located to a
relatively small distance from the power stations, is a very restrictive factor.
The Research Centre of Public Works (KEDE) has carried out significant
studies on the stabilization of aggregates and clayey soils, mainly with Portland
cement and with lime and fly ash since 1982. The exploitation of Megalopolis
fly ash and its applications in highway construction in adjacent areas has been
examined by Marsellos et al. [9]. Further studies have been undertaken by Greek
Universities, the Technical Chamber of Greece, and other researchers.
The main objective of this work is to test the capability of lime and fly ash in
improving the engineering properties of clayey soils from the areas of Thrace, in
order to use them as stabilized layers in road construction and to apply more
economic processes in constructing new pavements or improving existing ones.

2 Materials and methods


The soils used in this study have been sampled near the villages Aetolofos and
Aetokorifi of the Rhodope prefecture in Thrace. The soils are pleio-pleistocene
fluvio-lacustrine deposits resulted by the alteration of andesitic tuffs and tuffites
of the Zonaia Mountains surrounding the basin. These clayey soils are of black
colour near the surface, but they turn to grey or yellowish in the deeper horizons.
In some places they are intercalated by lenses or layers of sand and gravels.
Disturbed samples were taken from an excavation about 1 m deep in two
different locations, near the New Egnatia highway. The soil "S1" is a fine-grained
black clay, while the soil "S2" is a brown clay. Cation concentrations of Mg and
Ca 5.76 meq/l and 19.21 meq/l, respectively, have been determined for S1. The
respective values for S2 were 8.84 meq/l and 92.32 meq/l. The chemical
properties of the soils are summarized in Table 1.
Table 1:

Loss on Ignition
SiO2
Al2O3
Fe2O3
CaO
MgO
K2O
Na2O

Chemical composition of the soils tested.


Black Soil (S1)
11.62 (%)
64.18 (%)
12.73 (%)
5.43 (%)
1.55 (%)
1.50 (%)
1.80 (%)
0.70 (%)

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Brown Soil (S2)


14.95 (%)
57.25 (%)
11.97 (%)
5.43 (%)
7.28 (%)
1.16 (%)
1.55 (%)
0.21 (%)

330 Materials Characterisation V


The soils were air-dried and pulverized, in order to pass the o. 4 (4.75 mm)
sieve. The grain size distribution of the representative soil samples is presented
in Table 2.
Table 2:

Properties of natural soils.

Properties
Specific gravity (kg/cm2)
Liquid Limit (%)
Plastic Limit (%)
Plasticity Index (%)
Linear Shrinkage (%)
Free Swell Index (%)
Maximum Dry Density (kg/m3)
Optimum Moisture Content (%)
Grain Size Distribution
Sand and Gravels (%)
Silt (%)
Clay (%)
Classification
AASHO
USCS
Unconfined Compressive Strength (kg/cm2)

Soils
Black Soil (S1) Brown Soil (S2)
2.5
2.7
76
51
29
23
47
28
13.3
10
95
51
1588
1707
21.7
17.8
24.3
22.7
53.0

16.2
35.8
48.0

A-7-6
CH
1.5

A-7-6
CL
2.7

The basic properties of the soils were determined from representative samples
and for the soil fraction passing the o 40 (425 ) sieve. The liquid limit of these
soils was found using the Casagrande method.
The grain size distribution of the soils has been determined by both the dry
method (AASHTO T-27) and hydrometer analysis. The physical properties of
the soils studied and their unconfined compressive strength (UCS) are presented
in Table 2.
Both soils are classified as Group A-7-6 according to the AASHO
classification system, while, according to the Unified Classification System, are
classified as CH and CL respectively. Soil samples passing the No 4 (4.75 mm)
sieve were used in order to find the dry density-moisture content relation with
the standard Proctor compaction test. The soils were thoroughly mixed with
different moisture contents (14% to 30%) and were cured in a moisture room for
24 hours before they were compacted, for uniformity purposes. The maximum
dry density and the optimum moisture content are shown in Table 2.
The lime used in this study was a typical commercial hydrated calcitic lime,
having a high CaO content (65.25%). It was supplied by the AIMOS Lime
Company, Drama, Greece which has a 200 ton daily production. The chemical
composition of this lime is shown in Table 3.
The term fly ash represents the fine-grained ash residue produced from
pulverized coal combustion and carried away by the hot gases comes out of the
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Materials Characterisation V

331

chimney. This residue is usually collected with appropriate filter put along the
chimney. The fly ash used for the preparation of the laboratory specimens was
supplied by the Ptolemaida Power Station (6,000,000 ton/year). The chemical
composition of the fly ash is shown in Table 3.
Table 3:
Properties
Loss on Ignition
SiO2
Al2O3
Fe2O3
CaO
MgO
K2O
Na2O

Chemical composition of lime and fly ash.


Lime
33.25 (%)
0.01 (%)
0.01 (%)
0.11 (%)
65.25 (%)
0.50 (%)
0.01 (%)
0.01 (%)

Fly ash
13.90 (%)
29.95 (%)
10.85 (%)
4.57 (%)
20.00 (%)
1.90 (%)
0.95 (%)
0.32 (%)

3 Treatment of soil samples with lime and fly ash


The air-dried soil materials passing the No. 4 (4.75 mm) sieve, were mixed in
different proportions by weight with lime (in powder form) and fly ash. Water
was added until the optimum moisture content was reached and the mixing
process continued till a visually uniform product was achieved. Cylindrical
specimens 50 mm in diameter and 100 mm high were then formed in special
moulds. The material was placed in the mould in three layers of equal thickness.
The quantity of the material for each sample was determined by the optimum
moisture-maximum dry density relationship. The compaction to the maximum
dry density Proctor was achieved by compressing the required mass in the given
volume with an automatic hydraulic press. After their extraction from the mould,
the specimens were weighted and sealed in polyethylene bags, in order to keep
the moisture content constant during the curing period.
For each percentage of additive a set of three specimens was prepared. Care
was taken to cure the specimens under stable temperature and moisture
conditions. The specimens for the unconfined pressure test were cured for 7, 28
and 90 days before their testing.
The additivesoil weight ratios used were:
a) for the lime: 4100, 7100, 10100 for both soils.
b) for the fly ash: 4100, 8100, 12100.
Specimens were also prepared with limeflyashsoil ratios: 13100, 26
100 and 15100 by weight.
For each discrete ratio, the optimum moisture content was determined using
the standard Proctor method according to the AASHTO T99 61 specification.
The specimens were tested in an unconfined compression machine with strain
rate 1.25 mm/min.
An X-Ray Diffraction analysis showed that soil S1 had more swelling clay
minerals, while soil S2 had more kaolinite and calcite.
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332 Materials Characterisation V

4 Results and discussion


The Atterberg limits, the optimum moisture content and the maximum dry
density of the soil-lime, soil-fly ash and soil-lime-fly ash mixtures are presented
in Tables 4 and 5 for the black soil S1 and the brown soil S2 respectively. In the
same tables the unconfined compressive strength after 7, 28 and 90 days of
curing is shown.
The addition of lime resulted in a reduction of the liquid limit in comparison
with the natural soil. This fact complies to the results obtained by other
investigators (Sridharan et al. [10], Akoto [11], Athanasopoulou [12]) who have
observed a significant reduction in the LL of fine-grained soils following their
treatment with additives. The admixture of lime rapidly initiates flocculation and
cation exchange reactions, leading to a reduction of the specific area of the soil.
The reduction of the thickness of the diffused double layer causes the reduction
of the liquid limit. This reduction was smaller (12% with fly ash and 18% with
lime) for the brown clay, in comparison to the black soil (22% with fly ash and
27% with lime) due to higher concentration of calcium and magnesium
exchangeable cations and the lower percentage of swelling clay.
The admixture of lime and fly ash resulted in a reduction of the maximum dry
density (MDD) of the soils. On the other hand, an increase in optimum moisture
content (OMC) was observed for the same compaction effort (Tables 4 and 5).
The reduction in maximum dry density, following the treatment with lime and/or
fly ash, reveals the increased resistance to the compaction effort offered by the
flocculated soil-structure.
Table 4:

Alteration of properties of black clay treated with lime and fly ash.

Materials
Soil
g
100
100
100
100
100
100
100
100
100
100

F.A Lime
G
g
0
0
4
0
8
0
12
0
0
4
0
7
0
10
3
1
6
2
5
1

LL
%
76
69
64
59
68
60
55
66
65
59

Atterberg
Limits
PL
%
29
32
35
39
39
41
43
34
48
42

PI
%
47
37
29
20
29
19
12
32
17
17

Compaction
Characteristics
M.D.D. O.M.C.
%
Kg/m3
1588
21.7
1526
25.6
1487
26.4
1422
31.2
1453
28.8
1449
29.4
1445
29.9
1476
28.2
1453
29.4
1468
28.8

7
Days
1.5
4.3
6.4
7.6
6.0
6.5
7.4
3.3
7.9
3.8

UCS
(kg/cm2)
28
90
Days Days
1.5
1.5
4.5
5.6
7.2
7.9
8.8
9.5
9.6
13.6
11.7 22.9
13.5 16.4
4.1
5.0
9.3
11.7
4.3
4.3

The OMC increased as a consequence of the excess of water retained in the


voids of the flocculated soil-structure (formation of soil aggregates), which
results from the soil-additive interaction. For all the percentages of additive, the
mixtures with fly ash showed greater MDD values than those with lime, due to
the smaller apparent unit weight of lime.
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Materials Characterisation V

Table 5:

333

Alteration of properties of brown clay treated with lime and fly ash.

Materials
Soil F.A. Lime
g
G
g
100 0
0
100 4
0
100 8
0
100 12
0
100 0
4
100 0
7
100 0
10
100 3
1
100 6
2
100 5
1

LL
%
51
50
47
45
49
47
42
46
43
40

Atterberg
Limits
PL
%
23
33
37
40
NP
NP
NP
43
42
39

PI
%
28
17
10
5
---3
1
1

Compaction
UCS
Characteristics
(kg/cm2)
M.D.D. O.M.C.
7
28
90
kg/m3
%
Days Days Days
1707
17.8
2.7 2.7
2.7
1611
22.1
3.8 4.3
4.5
1577
24.5
6.6 7.9
9.2
1477
28.1
8.8 9.5 12.4
1575
24.6
3.5 5.7
8.5
1559
25.1
3.9 5.8
9.0
1525
26.5
3.9 6.0
8.4
1604
22.6
5.3 6.1
7.1
1558
24.9
8.4 11.7 12.6
1573
23.9
6.3 7.5
8.9

The change of OMC and MDD was gradual when fly ash was used, whereas
with the admixture of lime a rapid change existed with small percentages of
additive and remained almost constant thereafter. This could be attributed to the
reaction rate between the clayey soil and lime, as well as to its quick flocculation
due to quick exchange of soil cations with Ca++ from the lime and depression of
the double layer. On the other hand, the end change of these properties is greater
with fly ash than with lime due to the reaction of the soil with the constituents of
fly ash other than CaO, like SiO2, Al2O3 and MgO.
Considering the strength change of the soils, the UCS increased both with the
percentage of the additive and with the time of curing as it is demonstrated in
figures 1 to 4. In the case of lime addition, a dramatic increase occurred in the
strength of the soil (more than 10 times) with addition of only 4% lime. This
high rate of increase in soil strength was reduced with the increase of lime
content and at some 8-10% of lime the UCS remained more or less constant or
started to decrease (point of soil satisfaction). This percentage is recognized as
the lime modification optimum (LMO) of the soil. The same trends hold true for
the fly ash, though the rate of increase was lower and there was no point of soil
satisfaction. The strength increased in an almost constant rate when the
percentage of fly ash in the mixture was increased. As it is shown in figures 1 to
4 the rate of strength gain and the ultimate strength were different for both the
additive and the soil. Lime proved to be much more effective than the fly ash in
the case of the soil S1; the opposite has been observed for the soil S2.
The difference in the soil behaviour is certainly due to the differences in the
mineralogy of the soil and the kind of the exchangeable cations present. The
brown soil S2 is almost saturated by Ca++ cations, therefore the addition of lime
has little effect on the exchangeable cations of the soil. It is well-known that lime
has a more pronounced effect on swelling clay minerals (illite, caolinite) due to
the greater depression of the double layer. For the same reasons, fly ash yielded a
little better results in soil S1 than in the brown soil S2.
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334 Materials Characterisation V

Unconfined Compressive Strength (kg/cm2)

24

20
90 D-L

16

28 D-L

12

8
7 D-L

90 D-FA
28 D-FA
7 D-FA

4
Additive: Fly Ash
Additive: Lime

0
0

Figure 1:

6
8
10
Percent Additive (%)

12

14

16

Variation of UCS with the percentage of additive (Black clay, S1).

Unconfined Compessive Strength (kg/cm2)

14
90 D-FA

12
10

28 D-FA
90 D-L

7 D-FA

8
6

28 D-L

7 D-L

2
Additive: Fly Ash
Additive: Lime

0
0

Figure 2:

6
8
10
Percent Additive (%)

12

14

16

Variation of UCS with the percentage of additive (Brown clay, S2).

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Materials Characterisation V

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25
Soil Sample S1
Additive: Fly Ash
Additive: Lime
Additive: Lime+Fly Ash

7%

Unconfined Compressive Strength (kg/cm2)

20

10%

15
4%

2:6

10
12%
8%

4%

1:5
1:3

0%

0
7

28

49

70

91

Curing Period (days)

Figure 3:

Variation of strength values for mixtures after different curing


periods (Black clay, S1).

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336 Materials Characterisation V


15
Soil Sample S2
Additive: Fly Ash
Additive: Lime
Additive: Lime+Fly Ash

2:6

Unconfined Compressive Strength (kg/cm2)

12%

10
8%

7%

10%
4%

1:5
1:3

5
4%

0%

0
7

28

49

70

91

Curing Period (days)

Figure 4:

Variation of strength values for mixtures after different curing


periods (Brown clay, S2).

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Materials Characterisation V

337

Considering the effect of the curing period, the results followed the same
general pattern as with the percentage of additive. That is, for soil S1, the effect
of time was more significant in the case of lime than in the case of fly ash,
whereas in soil S2 the UCS value raised much more with the curing time when
fly ash was added than in the case where lime was used.
This difference could also be attributed to the abundance of swelling minerals
in soil S1. The more the swelling minerals, the more lime is precipitated in the
clay surface and the more cementitious materials (CaCO3) are formed. The
increase of strength in swelling minerals is due rather to cation exchange
(flocculation of the clay) and to the cementitious reaction than to the pozzolanic
one (Xeidakis [13], Baykal et al. [14]).
Soil mixtures having limefly ash ratios of 13 and 26 have given a little
higher strength values than those of the mixture with each additive alone. So, the
26 limefly ash ratio resulted to a strength two times and 1.5 times greater than
that with the addition of fly ash alone and lime alone, respectively (figures 3 and
4). The soil-lime-fly ash mixtures exhibited final strength values intermediate to
those found for the soil-lime and soil-fly ash mixtures.

5 Conclusions
The admixture of lime and fly ash to two expansive clays have led to a
significant decrease of the liquid limit probably due to the depression of the
diffuse double layer thickness associated with the clay particles, the aggregation
of the clay and the coating by Ca(OH)2.
A progressive reduction in maximum dry density and increase in optimum
moisture content has been observed with the addition of these materials. The
decrease of maximum dry density of clay soils, after their treatment with lime
and fly ash, is an indication of the increase of the strength of the soil and the
increase of its bearing capacity.
The strength of the mixtures tested was much higher than that of the natural
soils, in all cases. In general, the strength of soil-fly ash and soil-lime mixtures
increased with an increase in the additive content, for all curing periods. For both
soils and additives, an increase in curing period resulted to an increase in
strength.
The increase of the UCS for the soil S1 was greater with the addition of lime
(up to 20 times greater than the original), than with the addition of fly ash. The
best results obtained when 7% lime was added to the soils and a 90 days curing
period followed the compaction of the specimens. This is attributed to less Ca++
and a greater percentage of clay minerals in this soil. The strength increase in
soil S2 was greater with fly ash than with lime. This may be due to a higher
content in Ca++ and caolinite, as well as to a lower content in swelling minerals.
The results showed that the mineralogy of the soil plays a decisive role in the
stabilization process and greatly affects the ultimate strength of the mixture.
The ultimate strength of the soil after its improvement is adequate for the soil
to be used as subgrade or embankment material in main roads, or even as
subbase in some secondary roads.
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338 Materials Characterisation V

References
[1] Bell, F.G., An Examination of the Use of Lime and Pulverized Fly Ash to
Stabilize Clay Materials. Bulletin of the Association of Engineering
Geologists, XXX(4), pp. 469-479, 1993.
[2] Zhang, J. & Cao, X., Stabilization of Expansive Soil by Lime and Fly Ash.
Journal of Wuhan University of Technology - Mater. Sci. Ed. 17(4), pp.
73-77, 2002.
[3] Arora, S. & Aydilek A.H., Class F Fly-Ash-Amended Soils as Highway
Base Materials. J. Mat. in Civ. Engrg., 17(6), pp. 640-649, 2005.
[4] oka, E., Use of Class C fly ashes for the stabilization of an expansive
soil. Journal of Geotechnical and Geoenvironmental Engineering, 127(7),
pp. 568-573, 2001.
[5] Hesham, A.H.I., Treatment and improvement of the geotechnical properties
of different soft fine-grained soils using chemical stabilization. PhD.
Thesis, Martin Luther Halle-Wittenberg University, Germany, p. 182, 2006.
[6] Adu-Gyamfi, G., A Generalized theory for fly ash modified soils. Ph.D.
Thesis, Department of Civil Engineering and the Russ College of
Engineering and Technology, p. 247, 2006.
[7] Brooks, R.M., Soil stabilization with fly ash and rice husk ash.
International Journal of Research and Reviews in Applied Sciences, 1(3),
pp. 209-217, 2009.
[8] Ingles, O.G. & Metcalf, J.B., Soil Stabilization, Butterworths, Melbourne,
1972.
[9] Marsellos, N., Christoulas, S. & Kolias, S., Use of Fly Ash In Road
Construction. KEDE Bulletin, 3-4, Athens, 1986.
[10] Sridharan, A., Rao, S.M. & Murthy, N.S., Liquid Limit of Montmorillonite
Soils. ASTM Geotechnical Testing Journal, 9(3), pp. 156-159, 1986.
[11] Akoto, B.K.A., Influence of Flyash on the Strength Characteristics of LimeLaterite Soil Mixtures. Australian Road Research 18(4), pp. 224-231, 1988.
[12] Athanasopoulou, A., Improvement of the Mechanical Properties of
Materials Used in Earthworks and Pavements. Application to Soils
Encountered in the Area of Thrace, Ph.D. Dissertation, Department of Civil
Engineering, Democritus University of Thrace, p.569, 1995.
[13] Xeidakis, G.S., Assessment of the engineering and other properties of
expansive soils by various methods. Ph.D. Thesis, Dept. of Civil
Engineering, University of Leeds, England, 407 p., 1979.
[14] Baykal, G., Arman, A. & Ferrell, R., Accelerated Curing of Fly Ash-Lime
Mixtures. Transportation Research Record, 1219, pp. 82-92, 1989.

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Materials Characterisation V

339

Characteristics of a bolted joint with a


shape memory alloy stud
N. Ould-Brahim, A.-H. Bouzid & V. Brailovski
cole de Technologie Suprieure, Montreal, Canada

Abstract
Creep is an important factor that contributes to the load loss and tightness failure
of bolted joints. Retightening of the joint can be expensive, time consuming and
therefore is an undesirable solution. Currently most efforts are focussed on
reducing load losses directly by tightening to yield, improving material creep
properties or making joints less rigid. An alternative solution of current interest
is the use of bolts in shape memory alloy (SMAs). However, very few
experimental studies are available that demonstrate its feasibility. The objective
of this study is to exploit the benefit of the shape memory and superelasticity
behaviors of a SMA stud to recover the load losses due to creep and thermal
exposure of a gasket in a bolted joint assembly. This paper explores several
avenues to investigate and model the thermo-mechanical properties of a bolted
joint with a Nickel-Titanium SMA stud. A stiffness-based analytical model
which incorporates the Likhachev model of SMA is used as a representation of
an experimental bolted joint assembly. Using this model the rigidity of the
experimental setup is optimized to make the best use of the SMA properties of
the stud. This theoretical model is validated by a Finite Element (FE) Model
using a custom FE material model which also implements the SMA material
model. Finally an experimental test bench with an optimized stiffness derived
from analytical simulations is used, with and without gaskets to demonstrate the
ability of the SMA stud to recover load losses.
Keywords: shape memory alloys, bolted joints, creep, superelasticity, SMA.

1 Introduction
Load losses due to creep in any bolted joint can be problematic, even small creep
losses of 0.1mm, can cause a total loss of bolt load. Several methods are in use to
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340 Materials Characterisation V


attempt to reduce these losses, including tightening to yield, using gasket
materials or designs that reduce creep losses, or using less rigid joints. Some
research has been done in the use of Shape-Memory-Alloys in a bolted joint in
different ways. Peairs et al. [1], conducted research in using a thick SMA washer
in a bolted assembly based on a piezo crystal to qualify the load in the joint.
When a load loss is detected in the joint a heating element would activate the
SMA washer. They demonstrated that load recovery was possible, however due
to the nature of piezoelectric crystals the actual load in the joint and the
percentage load gained was not determined. Antonios et al. [2] as well as Hesse
et al. [3] tested a thick SMA washer with a load cell. Based on the same concept
of heating the element when a load loss was detected they succeeded in
recovering the load using the SMA washer. Labrecque et al. [4] used a Belleville
washer to recover load loss in a bolted joint, by electrically heating the washer
when the load was lost. The heating activated the washer, and generated
additional load, however after the cooling stage it was found that significant if
not all the total load was lost depending on the operating conditions. Ma et al. [5,
6] simulated the use of a bolted joint assembly to absorb seismic energy in
structural joints. The simulation was conducted primarily by FEM and
demonstrated the ability of SMA bolts to absorb significant stains and return to
their initial state, however no experimental work using SMA bolts was
conducted. Overall, the concept of using SMA in a bolted assembly has
undergone some experimental and theoretical research, however most of the
experimental work focuses on directly creating load losses by loosening the bolt,
and not by imposing creep losses. Furthermore the bulk of the experimental work
was conducted on SMA washers; however for the application of SMA bolts in
bolted joint assemblies, little experimental work is available in the literature.
This paper investigates the use of a Ni-Ti SMA stud in a bolted joint
assembly to recover creep losses. The research will focus on using the combined
effects of Shape Memory and Super-Elasticity (see Fig. 1) in order to recapture
load losses due to creep. First an analytical model is developed permitting a
quick evaluation of the behavior of SMA in a bolted joint. A finite element
model is also developed to demonstrate the ability of FEA to tackle more
complex joints such as with multiple bolts in SMA. These models incorporate
the Likhachev model of SMA [7], incorporated into MATLAB and ANSYS
through a user subroutine by Therriault et al. [8]. The models are then validated
against an experimental study of the use of a SMA bolt in a bolted gasketed
joint.

2 Analytical model
In order to make best use of the shape-memory and super-elasticity effects of the
nickel-titanium stud in the experimental test apparatus, a simplified analytical
model was implemented.
The model consists of 4 elements: The SMA stud, a spring element to
represent the stiffness of the test rig, a rigid element which is used to simulate

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Materials Characterisation V

341

the thermal expansion of the flange, and a creep element to simulate the
properties of the gasket.

Shape Memory Effect

Super-Elasticity

SMA Rod

SMA Rod at hot


temperature

Force applied

Force applied
Bent rod at low
temperature

Releasing force
returns rod to
undeformed shape

Heating returns rod


to original shape

Cold rod retains


old shape
Shape Memory effect can be used to
generate additional force if the rod is
constrained during heating

Super-Elasticity effect can be used to


recover stains with considerably less load
loss than conventional metals

Figure 1:

Schematic representation of shape memory and super-elasticity.

Equal Force and


Displacement Constraint
Spring Element
SMA Element

Thermal Expansion Element

Creep Element

Figure 2:

Analytical model.

The displacement obtained, along with the temperature is forwarded to the


SMA element, which yields a new force FSMA. This is converged iteratively for
each temperature or displacement change resulting in a 1D simulation of the
behaviour of the experimental rig.
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342 Materials Characterisation V


The Likhachev micromechanical model of SMA, implemented into a
numerical MATLAB [11] subroutine [8], was used in order to represent the
thermo-mechanical behaviour of the SMA Stud. The stiffness element, which in
the experiment consists of Belleville washers, is used to simulate the desired
flange assembly joint rigidity. The rigid element uses the thermal expansion
coefficient of steel and the clamped length of the modelled flange to determine
thermal strains of the model. Finally the creep element can use either a
logarithmic thermal creep law, experimental curve fits of creep data, or simply
consider a creep displacement linearly. Whereas the linear model does not give
an accurate time representation of creep over time, it gives accurate stresses and
strains before and after creep losses if the creep displacement is known.

Figure 3:

Effect of creep on SMA and steel bolt.

As shown in Fig. 2, there is considerable loss in bolt load during the heating
phase, before the austenitic transformation temperature. This is primarily caused
by the properties of the shape memory alloy stud. These properties can vary
considerably based on the heat treatment given and the nickel titanium ratios [9].
Using the linear creep model, a gasket creep displacement of 1 mm was
introduced during heating in a joint having an SMA bolt and compared to a joint
with a B7 steel bolt. It is clear that for large creep such as those expressed with
PTFE gaskets in industrial flanges, the SMA stud retains much higher loads than
the steel bolt.

3 Numerical FE model
The axisymmetric arrangement of the simulated flange with an SMA stud in the
center lends itself well to a 1 dimensional analysis which can be treated
analytically without great difficulties. However in order to model more complex
flanges and configurations with multiple bolts, and various non symmetric
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Materials Characterisation V

343

thermo-mechanical loading, requires a more detailed model. In order to


accomplish this modeling, a numerical FEM model was developed using
ANSYS workbench [10].
Rigid Nut
Steel Washer
Belleville Washer
Centering Plate
Flange
SMA element
Gasket creep induced
by displacement
constraint

Figure 4:

FE model of the experimental assembly.

The modeling of the shape memory behavior is accomplished using a user


subroutine material model that is incorporated to ANSYS [8]. This can
adequately represent the tension loads in a bolt. The advantage of using an FEM
model is that multiple SMA and non SMA bolts can be used in various
configurations to design and optimize a complex structure such as a bolted
flange which utilizes SMA to recapture creep losses.
Since the contact stresses between the metal elements do not greatly influence
the properties of the assembly, they were modeled using point constraints. This
results in a model of the experimental assembly which has a constant stiffness.
This model is then used to validate the analytical model, with excellent results as
the stiffnesss used are the same as shown in Fig. 5.

4 Experimental setup
The experimental test rig allows a gasket to be placed between two hollow
cylinders with a B7 steel bolt or an SMA bolt in the center. A cartridge heater is
placed around the assembly and the exposed surfaces are insulated to maintain an
even temperature distribution. The top flange is instrumented with a full strain
gauge bridge, calibrated to measure axial load. The SMA bolt is instrumented
with thermocouples and strain gauges, to ensure even temperature distribution
and measure the strain. Thermocouples are also used to measure air temperature
to control the heater and the temperature of the bolt.
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Stress(MPa)

344 Materials Characterisation V


400
350
300
250
200
150
100
50
0

ANSYSModel
MATLABModel

50

100

150

200

Temperature(C)
Figure 5:

Comparison of the analytical model and FEM variation of load


with temperature of the SMA bolt.
TopPlate

Thermocouples

CenteringPlates

TopFlange

Thermocouple

StrainGaugesfor
LoadDetermination

GasketPostion

BottomFlange

CenteringPlate

BottomPlate

SMA/B7Rod

Figure 6:

Strain Gauges

Experimental SMA bolt assembly.

5 Results and discussion


The experimental results are conducted in two stages. A small scale test using
wire samples of the SMA rod (from which the stud is machined) were conducted
by straining the samples to various strain levels, then heating them while
restraining the displacement, and measuring the force generated.
With this characterization available for small scale tests the Analytical and
Finite Element models can be supplied with the necessary information they
require to model the behavior of this specific sample of Ni-Ti alloy.

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Materials Characterisation V

400

5%elongation

3%elongation

345

7%elongation

Stress(MPA)

300
200
100
0
0

20

Figure 7:

40

60

80
100
120
Temperature(C)

140

160

180

200

Small scale characterization of SMA alloy.

30
NiTiSMABolt

B7SteelBolt

25

GasketStress(MPa)

20
15
10
5
0
0

Figure 8:

20

40

60

80
100
Temperature(C)

120

140

160

Comparison of the behavior of a B7 and an SMA stud in an


experimental bolted gasketed joint.

A 3/8 B7 Steel stud is compared to a SMA stud both loaded to a gasket


stress of 15MPa (2.1ksi) with a 1/8 expanded PTFE gasket. Both are then
heated to 150C (300F) and allowed to creep for one hour. The results are
compared and visibly demonstrate the advantages of an SMA bolt.
The gasket thicknesses were measured post test, and the SMA bolted joint
creeped 40% more than the B7 joint, likely due to the increased load. This
further shows the advantages of SMA since even with the additional creep, the
SMA bolt still generated a considerable amount of load, whereas the steel bolt
lost a considerable amount of load.
Comparing small scale test and experimental test rig results with Likachev
model results yields a good correlation between all 3. The experimental rig
results seem to generate higher loads than predicted. This is due to the residual
stresses generated by cutting the smaller wire samples from the rod, which has a
detrimental effect on their properties.

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346 Materials Characterisation V


600
5%elongation

SMABolt

LikachevModel

Stress(MPA)

500
400
300
200
100
0
0
Figure 9:

50

100

Temperature(C)

150

200

Comparison of small scale, experimental and numerical results.

6 Conclusion
In conclusion, preliminary results are promising and the use of a SMA rod has
considerably reduced the load loss due to creep in the gasket. It was also
demonstrated that additional load can be generated to further compensate creep
losses at higher temperatures. The application of the Likachev model of SMA in
both the analytical and FEM models yields good congruence with experimental
results.

References
[1] Peairs, D.M., Gyuhae Park; Inman, D.J., 2004, Practical issues of
activating self-repairing bolted joints, Smart Materials and Structures, v
13, n 6, p 1414-23,
[2] Antonios, C, Inman D.J, Smaili, A., 2006, Experimental and Theoretical
Behavior of Self-healing Bolted Joints, Journal of Intelligent Material
Systems and Structures, v 17, n 6, p 499-509,
[3] Hesse, T., Ghorashi, M., Inman, D.J., 2004, Shape memory alloy in
tension and compression and its application as clamping-force actuator in a
bolted joint, Part 1 experimentation, Journal of Intelligent Material
Systems and Structures, v 15, n 8, p 577-87
[4] Labrecque, C., Braunovic, M., Terriault, P., Trochu, F., Schetky, M., 1996,
Experimental and theoretical evaluation of the behavior of a shape
memory alloy Belleville washer under different operating conditions,
Electrical Contacts, Proceedings of the Annual Holm Conference on
Electrical Contacts, p 195-204.

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Materials Characterisation V

347

[5] Ma, Hongwei, Wilkinson, T., Cho, C., 2007, Feasibility study on a selfcentering beam-to-column connection by using the superelastic behavior of
SMAs, Smart Materials and Structures, v 16, n 5, p 1555-1563
[6] Ma, Hongwei, Cho, C., 2007, Application of superelasticity of SMAs in
bolted end-plate connection, Key Engineering Materials, v 353-358, pt.4,
p 3039-42.
[7] V.A. Likhatchev, V.G. Malinin, Structure-Analytical Theory of Strength,
Nauka, St-Petersburg, 1993 (in Russian).
[8] Therriault, P., Viens, F., Brailovski, V., 2006, Non-isothermal finite
element modeling of a shape memory alloy actuator using ANSYS,
Computational Materials Science, v 36, n 4, p 397-410.
[9] Brailovski, Vladimir, Prokoshkin, Sergei D., Khmelevskaya, Irina Yu.,
Inaekyan, Karine E., Demers, Vincent, Dobatkin, Sergei V., Tatyanin,
Evgeny V., 2006, Structure and properties of the Ti-50.0 at%Ni alloy after
strain hardening and nanocrystallizing thermomechanical processing,
Materials Transactions, v 47, n 3, p 795-804
[10] ANSYS, 2003, ANSYS Standard Manual, Version 11.0.
[11] Matlab, 2007, Version 7.4.0.287 (R2007a).

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Section 7
Thermal analysis

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Materials Characterisation V

351

Experimental validation of a thermal model of


adhesively bonded scarf repairs for CFRP
composite materials incorporating cure kinetics
C. C. N. Bestley, S. G. R. Brown & S. M. Alston
Materials Research Centre, College of Engineering,
Swansea University, UK

Abstract
Adhesively bonded scarf repairs are the preferred method of repairing modern
composite structures as they provide high strength restoration and aerodynamic
flushness. Curing of the adhesive bondline is carried out by locally heating the
repair area. To assess repair design and heating practices simulation can be used
to model both the transient heat transfer during curing and the level of cure likely
to be achieved at different regions in the adhesive joint. In this paper a 3D curing
model is described to simulate heat transfer through a composite component. The
cure kinetics of a commercial epoxy resin adhesive have been determined using
isothermal Differential Scanning Calorimetric (DSC) analysis. Using these
kinetics the model is able to determine the influence of the exothermic reaction
within the adhesive on the overall temperature variation within the component.
An experimental programme has been carried out where composite material and
bonded repair patches have been cured with thermocouples providing measured
temperature/time data during the cycle. The results from the cure model are then
validated by comparison with these experimental results. The cure model is
capable of being used to optimise the cure cycle for a bonded repair, ensuring the
maximum degree of cure of the adhesive with minimum variation of temperature
within the bond line.
Keywords: cure kinetics, DSC analysis, numerical model.

1 Introduction
The increase in use of composites in the aerospace, automotive and civil
engineering industries has led to the increasing demand for development of
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352 Materials Characterisation V


suitable repair methods [1]. Bonded repairs have been proven to restore strength
without compromising structural integrity [2]. In addition, the weight reduction
and aerodynamic properties of bonded repairs make them more favourable to
their bolted counterpart [3].
The mechanical properties of the adhesives used for bonded repairs are highly
dependent on the curing process [4,5]. Curing involves a complex set of
chemical reactions to elongate and crosslink pre-polymer molecules to form a 3D
molecular network. This is followed by the materials transition from a viscous
fluid to a viscoelastic solid [6].
Experimental investigation into the curing of composites produces the most
accurate and reliable results, although this is often expensive and time
consuming. As a result computational models are often used to simulate the
curing process. These models have the advantage of speed, low cost and the
ability to simulate ideal conditions.
Various studies have been conducted to simulate the curing process for thick
thermosetting matrix composites. Early work by Loos and Springer [7] formed
the basis for many of the cure models that followed. Their model simulated the
curing process of a flat plate in an autoclave using the finite difference method.
They were able to simulate residual stress development and void formation.
Later work by Bogetti and Gillespie [8] involved a two dimensional cure
simulation of a thick anisotropic thermosetting composite using thermal and
chemical kinetics. This model also used the finite difference method and was
based on the fundamental principles discussed in the Loos and Springer paper,
although with an added second dimension.
Zhu et al. [9] produced a three-dimensional cure model that simulated heat
transfer across a composite component, the cure process, residual stresses
developed and deformation. Finally, Cheung et al. [10] produced a threedimensional thermo-chemical cure simulation based on the Galerkin finite
element method. The rate and degree of cure throughout the curing process were
determined and induced residual stresses and the resulting deformation were
evaluated. This paper was the most influential in the formation of the cure model
used in this investigation.

2 Model description
A flat plate with dimensions of 560mm x 560mm with a uniform thickness of
10mm with a simple 120C cure cycle was simulated. The repair area consisted
of a patch of 260mm diameter with 5mm thickness and a 3 scarf angle.
The patch is bonded into the repair area using the same commercial film
adhesive as used in the DSC experiments. The cure cycle for this film adhesive is
provided by the manufacturer.
The equations were solved using a Gauss-Seidel algorithm where the
temperature and degree of cure were determined at each time step.
The cure kinetics equations in this work were based on the Cheung et al. [10]
paper and the heat transfer methodology is based on the work of Patankar [11]
entitled Numerical heat transfer and fluid flow.
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Materials Characterisation V

353

The three-dimensional time dependent energy balance equation is given as:


(1)
where is the density (kg m-3) , C is the specific heat capacity (J kg-1 K-1), k is
the thermal conductivity (W m-1 K-1) and T is the temperature (K). S is a source
term.
Discretisation of the time dependent energy balance equation forms the
following equation:
(2)
where:

(3-9)

The values of aE to aB represent the heat conductance between the grid point P
and the corresponding neighbour in the model where x, y and z represent the
dimensions of the control volume. The variable b is a constant consisting of the
internal energy and the rate of heat generation resulting from the term SC. This
term is given as:
where Q is the heat flow per unit mass (J/kg)

(10)

The harmonic means of the thermal conductivities were used to account for
the different materials used.
Finally the value of

TP is defined:
(11)

This is the temperature at grid point P.


The degree of cure, , is found to be related to the rate of reaction r by the
rate equation [10]:

(12)

This rate of reaction is given by the well established Kamal and Sourour [12]
equation:
1
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354 Materials Characterisation V


where K is the rate constant of the Arrhenius equation and m and n are constants
dependent on the resin system. The Arrhenius equation is used to determine the
rate of chemical reactions. It represents the dependence of the rate constant K of
chemical reactions on the absolute temperature T and activation energy E and is
given as:
(14)
where A1 represents the pre-exponential factor (sec-1) and E1 is defined as the
activation energy (J/mol). The rate constant, K, is the rate of reactions taking
place during cure and R is the universal gas constant. The values for these cure
kinetics and the value of Hr was found using Differential Scanning Calorimetry
(DSC).

3 Cure kinetics evaluation by DSC


Differential Scanning Calorimetry can be used to determine the glass transition
temperature (Tg) and degree of cure () of a commercial film adhesive by
measuring the heat flow into and out of a sample as it is heated (at a constant
heating rate) at a predefined temperature in a nitrogen purged atmosphere. This
method is based on the ASTM E698-05 [13] and involves the analysis of DSC
data at various heating rates to derive model-free kinetics.
Small samples (weighing approximately 20 mg) were placed in an aluminium
pan to be used in a Perkin Elmer Jade DSC. The sample was then rapidly heated
to a number of different temperatures. The exothermic reaction produced when
the adhesive cured was recorded and a normalised graph was produced of each
temperature.
The area under the exothermic peak was used to isolate data specific to the
cure of the adhesive, and this data recorded for each temperature provided the
degree and rate of cure (, /t respectively) at each time increment.

Figure 1:

Degree of cure of the epoxy film adhesive.

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Materials Characterisation V

355

The equation for the rate of cure has been given as:

(15)

where K1 and K2 are rate constants and m and n are reaction orders.
Further work using the DSC measurements showed the maximum degree of
cure does not reach 100% as towards the latter stages of the reaction it becomes
diffusion controlled. The current model was based on a final 100% cure for the
adhesive. Some models [14] have used a temperature dependent function max as
the maximum degree of cure to account for the diffusion controlled process in
the final stages of the curing reaction. This modification of the Kamal and
Sourour [12] equation is as follows:

(16)

This forms the basis for model 2 cure kinetics (see Table 1).
The least square best fit method can be used to minimise this difference
between the calculated and measured values by altering the values of K1, K2, m
and n. This produces fitted values of K1, K2, m and n for all temperatures which
can be used to find the cure kinetics of each model.

Figure 2:

Model 1 Arrhenius plot of rate constants lnK1 and lnK2 as a


function of cure temperature.

Arrhenius found that by taking the natural logarithm (ln) of both K1 and K2
and plotting them in a graph against the inverse of temperature (1/T) two linear
correlations are produced, with gradient and intercept of (-E/R) and A
respectively [15]:
ln

ln

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356 Materials Characterisation V


This method was then used to find the cure kinetics for model 2. The cure
kinetics for both models were found to be:
Table 1:
A1 (sec-1)

A2 (sec-1)
5

8.2985x10

3.435x1029

1.8294x10

12

4.8042x106

Cure kinetics.
E1 (J/mol)

E2 (J/mol)

72203

105960

1.1655

3.0108

257126

64296

0.8892

1.5493

These values were placed in the model to determine the effect of the
exothermic reaction during cure on the overall heat transfer through a composite
component.

4 Cure model results


A cell-centred finite difference model was formulated so that the component
geometry, cure cycle, the temperature of the local environment and insulation
could be changed with each simulation. This is so that the model can simulate
the bonding of repairs on different components in various conditions.
Experiments discussed later were based on some of these simulations, so that the
model could be validated.

Figure 3:

Model geometry (quarter).

The following table shows an example of the simulations used to determine


the effects of component thickness, ambient temperature and ramp rate.
Insulation effects were controlled by a change in heat transfer coefficient (HTC).
As expected, an increase in component thickness leads to an increase in
variation in temperature through the panel, particularly at the edges. An increase
in the surrounding temperature led to a more even distribution of heat through
the panel. An increase in ramp rate to the desired cure temperature also provided
a small improvement of heat distribution but did not significantly reduce the heat
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Materials Characterisation V

Table 2:
Model
No.
1
2
3
4

Cure
Temp
(C)
120
120
120
120

Thickness
(mm)
10
20
10
10

357

Model variations.
Ambient
Temperature
(C)
25
25
50
25

Rate
(C/min)

HTC
(Wm-2K-1)

1
1
1
3

15
15
15
15

lost through the edges of the panel. However, the effect of ramp rate on the
curing of the adhesive was significant. The increased ramp rate produced a far
higher degree of cure of the adhesive during the early stages of the cure cycle.

Figure 4:

Figure 5:

Degree of cure modelling.

Effect of Titanium bolt on .

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358 Materials Characterisation V


The influence of metallic components was investigated in the form of a
metallic bolt through the patch and surrounding structure. The bolt (assumed to
be manufactured from titanium) has a higher thermal conductivity than the
composite structure. However, the results from the simulation showed that the
presence of a metallic component increased the temperature of the local area by
an insignificant amount and the overall heat transfer through the component was
largely unaffected.

5 Experimentation
The model is based on the conduction of heat from a source above the
component. This is representative of a modern heating method used specifically
for repair of large composite components or for in-service applications. This
method involves a hot bonder used as the heat source of a number of CFRP
composite components of different thickness and geometry. These results were
used to validate the model and to suggest areas that required further
investigation.
Thermocouples were embedded into a 900mmx900mmx10mm panel in the
bottom right hand corner of the panel to match the model. Thermocouples 1-16
were placed after plies 8, 16, 24 and 32 in the arrangement shown in figure 6.

Figure 6:

Embedded thermocouple readings and layout.

The centre thermocouples demonstrated little variation in temperature and


were able to reach the desired cure temperature with ease. The thermocouples
closer to the edges exhibited a significantly lower temperature. The results of
these experiments were then compared with the cure model.

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Materials Characterisation V

359

6 Results and discussion


The thermocouple readings for this trial were comparable to the results produced
by the cure model. The panel was inadequately insulated at the edges to clearly
demonstrate heat loss through the edges and underside of the panel.
This resulted in heat lost through the edges of the panel, particularly in the
corner. The model was able to demonstrate this heat loss with a high degree of
accuracy.
The most significant modification was made to the heat transfer coefficient at
the edges and underside of the component. From experimental data and the
results from the model a small range of HTCs (between 10-20 Wm-2K-1) were
determined based on insulation and environmental temperature. This
demonstrates the effectiveness of insulation and the detrimental effect
environmental conditions can have on heat transfer through a composite
component.
The assumptions made in the formation of the cure model should be taken
into account when viewing the results.

Figure 7:

Corner view heat distribution.

For example, the thermal conductivity values for each material were
considered to be the same in all directions. In practice, the thermal conductivity
of carbon fibre in the transverse direction is approximately 25% of that in the
longitudinal and through-thickness directions [16]. However, the experimental
trials compare favourably with the results from the models.
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360 Materials Characterisation V

7 Conclusions
A finite difference model was produced to simulate heat transfer through a flat
CFRP composite panel during the cure cycle of a bonded repair process. The
effects of heating rates, insulation and environmental temperature were simulated
and the results validated through experimental investigation.
Further modification of the model from experimental results has improved
both the accuracy of the model and the ability to uniformly heat a composite
component. The results from the model have provided insight into the nature of
heat transfer under different conditions.
The large variance in temperature between the centre and edge thermocouples
was demonstrated in both the model and experimentation.
The model provided more information as to where the heat loss is most
significant, and with further trials in combination with further modelling this
heat loss could be significantly reduced.
The exothermic reaction during the cure of the adhesive was determined to
have an insignificant impact on the overall heat transfer through the component.
The incorporation of a Titanium bolt increased the local temperature and
therefore degree of cure of the adhesive in the early stages of the cure cycle.
However, this became insignificant towards the latter stages of the cure.
Ongoing work will involve the optimisation of the cure cycle for bonded
repair, residual stresses and deformation, and void formation.

Acknowledgements
This work was carried out as part of the CONTOUR project in collaboration with
Airbus Operations Limited under Welsh Assembly Government contract
reference number HE 09 COL 1030.

References
[1] Tomblin, J.S., Salah, L., Welch, J.M., Borgman, M.D., Bonded Repair of
Aircraft Composite Sandwich Structures, Final Report, DOT/FAA/AR03/74, Office of Aviation Research, Washington D.C. 20591, February
2004.
[2] Baker, G., Bonded Composite Repair of Fatigue-Cracked Primary Aircraft
Structure. Composite Structures, 47(1-4), pp. 431-443, 1999.
[3] Charalambides, M.N., Hardouin, R., Kinloch, A.J. Matthews,
F.L., Adhesively-Bonded Repairs to Fibre-Composite Materials
I: Experimental. Composites Part A: Applied Science and Manufacturing,
29(11), pp. 1371-81, 1998.
[4] Yi, S., Hilton, H. H., Ahmad M.F., A Finite Element Approach for Cure
Simulation of Thermosetting Matrix Composites. Computers & Structures,
64(1-4), pp. 383-388, 1997.

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Materials Characterisation V

361

[5] Stewart, I., Chambers, A., Gordon, T., The Cohesive Mechanical Properties
of a Toughened Epoxy Adhesive as a Function of Cure Level. International
Journal of Adhesion & Adhesives, 27(4), pp. 277-287, 2007.
[6] Yu, H., Mhaisalkar, S.G., Wong, E.H., Teh, L.K. & Wong,
C.C., Investigation of Cure Kinetics and Its Effect on Adhesion Strength of
Nonconductive Adhesives Used in Flip Chip Assembly. IEEE Transactions
on Components and Packaging Technologies, 29(1), pp. 71-79, 2006.
[7] Loos, A.C., Springer, G.S., Curing of Epoxy Matrix Composites. Journal of
Composite Materials, 17(2), pp. 135-169, 1983.
[8] Bogetti T.A., Gillespie, J.W., Two-Dimensional Cure Simulation of Thick
Thermosetting Composites. Journal of Composite Materials, 25(3), pp.
239-273, 1991.
[9] Zhu, Q., Geubelle, P.H., Tucker, C.L., Dimensional Accuracy of Thermoset
Composites: Simulation of Process-Induced Residual Stresses. Journal of
Composite Materials, 35(24), pp. 2171-2205, 2001.
[10] Cheung, A., Yu, Y., Pochiraju, K., Three-Dimensional Finite Element
Simulation of Curing of Polymer Composites. Finite Elements in Analysis
and Design, 40(8), pp. 895-912, 2004.
[11] Patankar, S.V., Numerical Heat Transfer and Fluid Flow, Taylor &
Francis: Oxfordshire, 1980.
[12] Kamal, M.R., Sourour, S., Kinetics and Thermal Characterization of
Thermoset Cure. Polymer Engineering & Science, 13(1), pp. 59-64, 1973.
[13] Standard Test Method for Arrhenius Kinetic Constants for Thermally
Unstable Materials Using Differential Scanning Calorimetry and the
Flynn/Wall/Ozawa Method, ASTM E 698-05, 2005.
[14] Lee, C.L., Wei, K.H., Curing Kinetics and Viscosity Change of a Two-Part
Epoxy Resin During Mold Filling in Resin-Transfer Molding Process.
Journal of Applied Polymer Science, 77(10), pp. 2139-2148, 2000.
[15] Lee, J.Y., Choi, H.K., Shim, M.J., Kim, S.W., Kinetic Studies of an Epoxy
Cure Reaction by Isothermal DSC Analysis. Thermochimica Acta, 343
(1-2), pp. 111-117, 2000.
[16] Mutnuri, B., Liang, R., GangaRao, H., Thermal Conductivity
Characterization of FRP Composites: Experimental. ANTEC, May 7-11,
Charlotte, NC, 2006.

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Materials Characterisation V

363

Computational and experimental


characterization of building envelopes based on
autoclaved aerated concrete
V. Ko, J. Vborn & R. ern
Department of Materials Engineering and Chemistry,
Faculty of Civil Engineering, Czech Technical University in Prague,
Czech Republic

Abstract
Hygrothermal performances of three types of building envelopes based on
autoclaved aerated concrete (AAC) provided with different thermal insulating
materials (expanded polystyrene, hydrophilic mineral wool, AAC with extended
thermal insulation capability) are compared. The simulations are accomplished
using the computer code HEMOT based on the finite element method. Results of
the simulation are the moisture and temperature fields across the building
envelope, which in combination with mechanical parameters present a sufficient
data source for service life analysis.
Keywords: computational analysis, coupled heat and moisture transport,
autoclaved aerated concrete, building envelopes, climatic conditions.

1 Introduction
Autoclaved aerated concrete (AAC) is a structural material which is commonly
used around Europe, particularly as it combines ease of construction with
excellent combination of its mechanical and thermal properties. However,
despite the very good thermal properties of AAC, it can be anticipated that with
the increasing demand for energy savings it will become a necessity to provide it
with thermal insulating system or at least very good thermal insulating plaster to
meet stringent conditions given by future thermal standards. The choice of
proper insulating material for AAC is though quite difficult with respect to
service life of the whole building envelope. As it was demonstrated in [13],
most common insulation materials cause extreme hygrothermal straining of
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364 Materials Characterisation V


external finishes so it is necessary to choose wisely. The proper method, how to
compare the results is to use computational tool for simulating coupled heat and
moisture transport in multi-layered systems of porous building materials. One of
such tools which were already successfully tested in previous calculations is
HEMOT developed at the Department of Materials Engineering and Chemistry,
Faculty of Civil Engineering, Czech Technical University in Prague. This
computer code which will be employed in this paper uses Knzels mathematical
model for coupled heat and moisture transport. The equations are solved using
finite element method.

2 Computational analysis
The computer code HEMOT [4] is based on the general finite element package
SIFEL [5]. As basic input parameters of the mathematical model, hygric, thermal
and basic physical parameters of used materials, construction detail, initial and
boundary conditions and time specification of simulation are required.
Description of all input parameters in more detail is given later.
In the computer simulations we focused on a comparison of hygrothermal
behavior of several building envelopes based on AAC provided with different
thermal insulating materials.
2.1 Mathematical model
Knzels mathematical model of heat and moisture transport [6] was used in the
simulations which can be formulated as

d v
div D grad p grad ps
d t

(1)

dH T
divgradT Lv div p grad p s
dT t

(2)

where v is the partial density of moisture, relative humidity, p permeability


of water vapour, ps partial pressure of saturated water vapour, H enthalpy
density, Lv heat of evaporation of water, thermal conductivity and T
temperature,

D Dw

d v
d

(3)

is liquid moisture diffusivity coefficient, Dw capillary transport coefficient.


2.2 Scheme of construction detail
Three variations of building envelope based on AAC were chosen for simulation,
in order to analyze the consequences of different material combinations. As a
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Materials Characterisation V

365

start-up building envelope we chose AAC without any external finish which
allowed us to get real image about hygrothermal performance of AAC layer itself
[7]. In the next simulation we provided AAC with hydrophilic mineral wool
(marked as Var. 1), expanded polystyrene (Var. 2) and Multipor Ytong produced
by Xella CZ (Var. 3). All these envelopes were provided from interior and
exterior side with Baumit MVR Uni plaster which is recommended for AAC
structures as external finish. On the material interface between mineral wool and
AAC an adhesive mortar layer was placed. Description of used materials in more
detail is given in next subsection. Scheme of construction detail including the
dimensions of each layer is shown in Figure 1. In all investigated variations we
focused on the hygrothermal conditions at points within the AAC layer and
external plaster just 2 mm under its external surface which can be considered as
characteristic position from the point of view of possible frost damage.

Figure 1:

Scheme of AAC-based building envelope.

2.3 Material parameters


Aerated autoclaved concrete P4-500 produced by Xella CZ was under
consideration in this paper as the load-bearing material. For exterior and interior
renders we used Baumit MVR Uni Plaster, which is single-layer plaster for
exterior and interior surfaces especially recommended for AAC. As the thermal
insulation we assumed Rockwool hydrophilic mineral wool, expanded
polystyrene and Multipor. For adhesive layer between AAC and mineral wool
we used Mamut M2 mortar.
All the material parameters were measured in laboratory of transport
processes at the Department of Materials Engineering and Chemistry, Faculty of
Civil Engineering, Czech Technical University in Prague [811] and are
summarized in Table 1 and Figure 2. Data for Mamut M2 mortar were measured
by M. Jerman and have not been published yet. We used these symbols: bulk
density [kg/m3], mat matrix density [kg/m3], porosity%], c specific heat
capacity [J/kgK], water vapour diffusion resistance factor [-], w moisture
content by volume [m3/m3], thermal conductivity [W/mK], moisture
diffusivity [m2/s].
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366 Materials Characterisation V


Table 1:
Parameter

AAC
P4-500

Mamu
t M2
mortar

[kg m-3]
%]
c [J kg-1 K1
]
[-]

500

dry [W m-1
K-1]
sat [W m-1
K-1]
[m2 s-1]

Expanded
polystyrene

Multip
or

1430

Hydrophi
lic
mineral
wool
71

50

125

Baumit
MVR
Uni
plaster
1402

80.2
1020
1510
3.0 9.7

42.6
1020

96.0
810

97.0
1300

12.4

4.3

50

0.114

0.481

0.043

0.040

94.2
2230
3500
1.9
10.9
0.047

44.4
1020 1780
4.5
12.4
0.443

0.454

2.022

0.246

0.560

0.166

1.380

Fig. 2

1.07e9
0.201

8.4e-6

2.10e-11

Fig. 2

1.59e-9

0.000046

0.001

0.0078

0.042

0.01846

whyg
[m3 m-3]

Material characteristics.

Moisture diffusivity [m2/s]

1.00E-05

1.00E-06

1.00E-07

1.00E-08

AAC P4-500
Multipor
1.00E-09

1.00E-10
0

0.05

0.1

0.15

0.2

0.25

0.3
3

0.35

0.4

Moisture content by volume [m /m ]

Figure 2:

Moisture diffusivity.

2.4 Initial and boundary conditions and time interval of simulation


As the initial and boundary conditions climatic data in the exterior in the form of
Test Reference Year for Prague which contained average data for 30 years were
used. On the interior side constant value of relative humidity 55% and

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Materials Characterisation V

367

temperature 21C (see Fig. 3) was chosen. The simulation started on 15th July
and took 6 years. The final results show data obtained for the last year.

Figure 3:

Boundary conditions.

3 Computational results
The results of computational simulations are summarized in a set of figures
which describe hygric and thermal performance of studied material of building
envelope during a reference year. In all figures we focused on moments when
moisture content and temperature reached certain limits simultaneously. In case
of moisture content this limit was the value of hygroscopic moisture content (see
Tab. 1), in case of temperature the freezing point of water. When these two
conditions are fulfilled, contained liquid moisture is getting frozen. This leads to
consequent damage of material.
The materials capability to resist to freezing of contained water is
characterized by its freeze-thaw resistance which can be measured under
laboratory conditions [12]. This was accomplished for AAC and its freeze-thaw
resistance was set to 25 cycles [13]. Durability of AAC can be then calculated as
quotient of freeze-thaw resistance and number of freezing cycles appearing in the
material in building envelope during a year.
3.1 AAC wall provided with hydrophilic mineral wool
Hygrothermal performance of AAC and external plaster of building envelope
provided with hydrophilic mineral wool is captured in Figures 4 and 5.
The temperature in AAC block 2 mm under its external surface is lower than
in other investigated envelopes, but freezing point of water is not reached and
level of moisture content is deeply in underhygroscopic range. That means that
AAC block in not threatened by effects of freezing water.
Hygrothermal performance of exterior plaster is shown in Figure 5. Although
the temperature drops below zero many times during a reference year, this does
not happen simultaneously with moisture increase. So, there is not any water
which can freeze and damage the structure of plaster. During a reference year,
the overhygroscopic moisture content is reached only five times and only in
summer months. So we can summarize, that even in the plaster there are not any
freezing cycles.
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368 Materials Characterisation V


0.10
Temperature 273.15 K
Temperature
Hygroscopic moisture content
Moisture content

0.08

Temperature [K]

0.07

300

0.09

Moisture content [m /m ]

320

280

0.06
0.05

260
0.04
240

0.03
0.02

220
0.01
200
731

0.00
781

831

881

931

981

1031

1081

Time [days]

Figure 4:

Hygrothermal performance of AAC, Var. 1.


0.10
Temperature 273.15 K
Temperature
Hygroscopic moisture content
Moisture content

0.08

Temperature [K]

0.07

300

0.09

Moisture content [m /m ]

320

280

0.06
0.05

260
0.04
240

0.03
0.02

220
0.01
200
1700

0.00
1750

1800

1850

1900

1950

2000

2050

Time [days]

Figure 5:

Hygrothermal performance of exterior plaster, Var. 1.

3.2 AAC wall provided with expanded polystyrene


The results of hygrothermal performance of AAC wall provided with expanded
polystyrene are shown in Figures 6 and 7.
In AAC, the values of temperatures keep above 0C for all the year, the level
of moisture content stays in underhygroscopic range. It means that any single
condition for creation of freezing cycle is not fulfilled.
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Materials Characterisation V

369

0.10
Temperature 273.15 K
Temperature
Hygroscopic moisture content
Moisture content

0.08

Temperature [K]

0.07

300

0.09

Moisture content [m /m ]

320

280

0.06
0.05

260
0.04
240

0.03
0.02

220
0.01
200
1700

0.00
1750

1800

1850

1900

1950

2000

2050

Time [days]

Figure 6:

Hygrothermal performance of AAC, Var. 2.


0.10

Temperature 273.15 K
Temperature
Hygroscopic moisture content
Moisture content

320

300

0.09
0.08

0.06
0.05

260
0.04
240

Temperature [K]

Moisture content [m /m ]

0.07
280

0.03
0.02

220
0.01
200
1700

0.00
1750

1800

1850

1900

1950

2000

2050

Time [days]

Figure 7:

Hygrothermal performance of exterior plaster, Var. 2.

A different situation appears in exterior plaster as one can see in Figure 7.


There are few moments, when the level of moisture content reaches
overhygroscopic range for sufficiently long time. The most interesting moments
are these in winter, when the temperature drops below zero (around 1800th day of
simulation). In hygrothermal simulation of this type of building envelope, 15
freezing cycles per a year are counted in exterior plaster.
3.3 AAC wall provided with Multipor
Figures 8 and 9 capture hygrothermal performance of AAC and exterior plaster
of wall provided with Multipor.
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370 Materials Characterisation V


As in the previous variations, the hygrothermal performance of AAC is
similar. There are not any freezing cycles because of relatively high temperature
and low moisture content (see Figure 8).
0.10
Temperature 273.15 K
Temperature
Hygroscopic moisture content
Moisture content

0.08

Temperature [K]

0.07

300

0.09

Moisture content [m /m ]

320

280

0.06
0.05

260
0.04
240

0.03
0.02

220
0.01
200
1700

0.00
1750

1800

1850

1900

1950

2000

2050

Time [days]

Figure 8:

Hygrothermal performance of AAC, Var. 3.

In exterior plaster applied on Multipor insulation, 10 freezing cycles are


counted (see Fig. 9). Between 1789th and 1814th day of simulation the moisture is
in overhygroscopic range and at the same time the temperature drops below zero
so the condition for creation of freezing cycles is fulfilled.
0.10
Temperature 273.15 K
Temperature
Hygroscopic moisture content
Moisture content

0.08

Temperature [K]

0.07
280

0.06
0.05

260
0.04
240

0.03
0.02

220
0.01
200
1700

0.00
1750

1800

1850

1900

1950

2000

2050

Time [days]

Figure 9:

300

0.09

Moisture content [m /m ]

320

Hygrothermal performance of exterior plaster, Var. 3.

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4 Discussion
The protection of AAC walls against effects of weather conditions and freezing
water in particular is certainly a necessity. It was proved already in the previous
work [7]. There are two ways how to achieve that. The AAC wall can be
protected against increase of moisture content which can be accomplished by
suitable waterproof modification of external surface or we can protect the wall
against low temperatures using one of many thermal insulating materials. The
second possibility seems to be more advantageous with respect to stringent
conditions given by thermal standards which have to be met.
The advantage of thermal insulation applied on AAC is the fact that together
with frost the AAC is protected against moisture penetrating from exterior as
well. However, the application of thermal insulation goes along with negative
effects. One of the most significant is extreme straining of external finishes,
which are applied on. This was already indicated in [13] and also results
obtained in this paper confirmed it.
The main reason can be seen in the low moisture diffusivity of used thermal
insulating materials (expanded polystyrene, Multipor). This leads to slowing
down the moisture transport from exterior plaster towards the interior and to
moisture increase in plaster subsequently. Considering the direct exposition of
plaster to weather conditions, temperature in particular, water saturated plaster
can be then easily damaged by effects of freezing of contained liquid moisture. It
can be spoken in general, the lower moisture diffusivity of thermal insulating
material is, the more freezing cycles in exterior plaster will appear. In our case,
there were 15 freezing cycles in plaster applied on expanded polystyrene and 10
freezing cycles in plaster applied on Multipor and that corresponds to values of
moisture diffusivity.
Opposite situation occurred when hydrophilic mineral wool has been used.
Thanks to high moisture diffusivity of hydrophilic mineral wool, all the received
moisture can be quickly transported away, so the plaster stays relatively dry and
does not contain the liquid moisture. On the other hand, moisture content of
AAC is higher, which is obvious, when Figures 4, 6 and 8 are compared.
Although the moisture content is still very low, the total amount of moisture
contained in whole building envelope provided with hydrophilic mineral wool is
higher than in other studied cases so that the thermal insulating capability of that
building envelope may possibly decrease.

5 Conclusion
According to the results obtained in this paper, protection of AAC block in
building envelopes against weather conditions is a necessity. It can be
accomplished in many ways; one of the best seems to be using thermal insulating
materials from exterior side. In this paper, computational simulation of building
envelopes provided with different types of thermal insulating materials has been
accomplished. The best results were obtained when hydrophilic mineral wool
was under consideration. The other variants with expanded polystyrene or
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372 Materials Characterisation V


thermally insulation AAC material Multipor did not lead to suitable results. It
was caused by low value of moisture diffusivity which was the cause of increase
of moisture content in exterior plaster. The level of moisture content then
exceeded the hygroscopic limit and freezing of liquid water was allowed.
The building envelope with hydrophilic mineral wool showed different
hygrothermal performance. High value of moisture diffusivity of mineral wool
allowed water to be transported deeper into the envelope which led to decrease
of moisture content in external plaster. Protection against effects of freezing
water was sufficiently fulfilled. However, total moisture content in building
envelope was then higher.
In next research, it would be advisable to focus on design of new insulating
materials or modification of material parameters of current materials using
inverse analysis in order to find the composition of AAC-based building
envelope which will combine good frost resistance and good thermal insulating
properties as well.

Acknowledgement
This research has been supported by the Czech Science Foundation, under grant
No. 103/09/0016.

References
[1] Madra, J., Ko, V., Vejmelkov, E., ern, R., Rovnankov, P. et al,
Influence of material characteristics of concrete and thermal insulation on
the service life of exterior renders. In: Fourteenth International Conference
on Computational Methods and Experimental Measurements, Algarve,
Portugal. Wessex: WIT PRESS, p. 13-23. ISBN 978-1-84564-187-0. 2009.
[2] Madra, J., Ko, V., Koreck, T., ern, R. et al. Computational analysis
of hygrothermal performance of building envelope under different climatic
conditions In: Thermophysics 2010. Brno: University of Technology,
p. 180-187. ISBN 978-80-214-4166-8. 2010.
[3] Jerman, M., Ko, V., Madra, J., Vborn, J., ern, R, Water and heat
transport parameters of materials involved in AAC-based building
envelopes In: 1st Central European Symposium on Building Physics. Lodz:
Technical University of Lodz, p. 39-45. ISBN 978-83-7283-367-9. 2010.
[4] ern R., Complex System of Methods for Directed Design and
Assessment of Functional Properties of Building Materials: Assessment and
Synthesis of Analytical Data and Construction of the System. CTN CTU in
Prague, 192 201. 2010.
[5] Kruis, J., Koudelka, T., Krej, T., Efficient computer implementation of
coupled hydro-thermo-mechanical analysis. In: Mathematics and
Computers in Simulations, vol. 80, no. 8, pp. 1578-1588. ISSN 0378-4754.
2010.
[6] Knzel, H.M., Simultaneous Heat and Moisture Transport in Building
Components, Ph.D. Thesis, IRB Verlag: Stuttgart, pp. 1135, 1995.
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Materials Characterisation V

373

[7] Madra, J., Ko, J., Ko, V., Vborn, J., ern, R., Computational
prediction of hygrothermal conditions in innovated AAC-based building
envelopes. In: Advanced Computational Methods and Experiments in Heat
Transfer XI. Southampton: WIT Press, pp. 291-301. ISBN 978-1-84564462-8. 2010.
[8] Jiikov, M. and ern, R., Effect of Hydrophilic Admixtures on Moisture
and Heat Transport and Storage Parameters of Mineral Wool, Construction
and Building Materials, 20, 425-434, 2006.
[9] Vborn, J. Stanoven tepelnch parametr a smrtn pi vysychn
vybranch probetonovch tvrnic firmy H+H esk republika s.r.o. a
Xella CZ. In: Proceedings of the International Conference 15th
Construmat 2009. Praha: esk vysok uen technick v Praze, pp.
449-461. 2009.
[10] Fukov, L., Moisture Properties of AAC Blocks in dependence on the
Environment Focused on Problems with Durability. Diploma thesis. Praha:
Czech Technical University in Prague, 2009.
[11] Jerman, M., Vborn, J., ern, R., Tepeln a vlhkostn charakteristiky
novch probetonovch vrobk, In: Stavebn obzor, ro. 20, . 1, s. 7-11.
ISSN 1210-4027. 2010.
[12] SN EN 15304. Determination of the freeze thaw resistance of
autoclaved aerated concrete. Praha: Czech Standards Institute, 2007.
[13] Vborn, J., Testing of the Drying Shrinkage and Freeze - thaw Resistance
of Autoclaved Aerated Concrete. In: XII International scientific conference
Technick zazen staveb a energie budov. Brno: Akademick
nakladatelstv CERM, pp. 215-218. 2009.

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Section 8
Recycled materials

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Materials Characterisation V

377

Quantitative description of the morphology


of polyurethane nanocomposites for
medical applications
J. Ryszkowska & B. Waniewski
Warsaw University of Technology,
Faculty of Materials Science and Engineering, Poland

Abstract
This paper presents the application of stereology methods to the description of
morphological properties of polyurethane nanocomposites for medical
applications. The study of the cross-section surface structure of the obtained
materials was performed by Atomic Force Microscopy. The volume of hard
phase agglomerate was used to evaluate the degree of phase separation of the
examined nanocomposites. The relationships between the domain agglomerate
characteristics and the properties of nanocomposites obtained from them were
analysed.
The results showed that nanocomposites with non-modified nanosilica
dioxide (SiO2) and nanosilica dioxide modified with NH2 groups differs from
polyurethane within the following properties: size and volume of the
agglomerates of the hard domains, biocompatibility, thermo-mechanical and
abrasive wear resistance.
Keywords: nanocomposites, polyurethane, structure, image analysis, biomedical
application

1 Introduction
Polyurethanes (PURs) and their nanocomposites are a versatile plastic material,
formulated to provide good biocompatibility, flexural endurance, high strength,
high abrasion resistance and processing versatility over a wide range of
applications [1]. The most common use in medical devices is in short-term
implants [2]. Polyurethane elastomers are linear segmented copolymers
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378 Materials Characterisation V


consisting of a relatively flexible component derived from a macrodiol called
soft segment, and a relatively hard and stiff component derived from a
diisocyanate and a chain extender called hard segment (Fig 1). Thermodynamic
incompatibility of these segments leads to microphase separation. The domain
structure formed by microscopic phase separation presents similar elastomeric
properties to those shown for cross-linked rubber networks. The mechanical
strength of this structure can be attributed to hard microdomains physically
cross-linked through hydrogen bonding and dispersion forces, acting as fillerlike reinforcement for the soft segment [3]. Polyurethanes are characterized by a
complex morphology which is dependent upon the precise nature of the hard and
soft segments and their composition, use of nanoparticles, preparation method
and its parameters. All these factors influence the morphological factors such as
degree of microphase separation, crystallinity, the domain agglomerate
characteristics, and define properties such as hardness, stiffness, tensile strength,
clarity and biocompatibility [17].

Figure 1:

Domains structure of polyurethane.

This paper presents the application of stereology methods to the description


of morphological properties of polyurethane nanocomposites for medical
application. Stereological parameters [810] chosen for analysis were used to
evaluate the degree of phase separation of the examined nanocomposites.
Relationships between the domain agglomerate characteristics and the properties
of the nanocomposites obtained from them were analysed.

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379

2 Experimental
2.1 Materials
The following reactants were used in the synthesis of PURs:
polyoxythetramethylene glycol (PTMG) of molecular weight 2023 g/mol
(Therathane 2000) was supplied by Du Pont Nemours Co. ; 4.4diphenylmethane diisocyanate (MDI) purchased from Aldrich Chemical Co.
(Germany); ethylene glycol (GE) and glycerine (G) POCH (Gliwice, Poland).
Polyol was dehydrated by mixing under vacuum for 2h at 120C. Ethylene
glycol and glycerin was dried under a molecular sieve.
Nanosilica powder and nanosilica powder modified with NH2 groups, with
primary particle size of 75 nm were used as nanofiller (ICHP Warsaw). To
prepare the composites, nanosilica polyetherodiols 20% wt. concentrate was
made. Firstly, polyetherodiol was melted down in the oven under 80C degree.
Then nanosilica was put into it and mixed with ultrasonic homogenizer VCX
750 by Sonics during 30min in pulse mode 3/3 (3sec mixing, 3sec stop).
2.2 Polyurethane and nanocomposites synthesis
Segmented polyether based polyurethanes with substrates molar ratio PTMG:
MDI: GE: G equal to 40:80:27:24 (1:2:0.679:0.151), constant isocyanates index
of 1.05 and with hard segment contents 20 wt.% was synthesized using a onestep polymerisation method. The polyol was cooled to 70C3C, with glycol
added and glycerin blended for 5min. Then the mixture was cooled to 60C3C
and MDI added. The samples were obtained with free casting method. The heat
up process was carried out in the oven for 16 hours. To prepare the composites,
appropriate quantities of concentrate were added to the polyol. The mixture was
dehydrated in temperature of 120C5C under 2-5 hPa pressure. Next the
process was run in the same way as polyurethane synthesis. Description of
achieved materials is presented in Table 1.
Table 1: Description of the achieved materials.
Sample
Amount of nanofiller [wt.%]
Modification of nanofiller

0
0
-

1
0.5
-

2
1.0
-

3
2.0
-

1A
0.5
-NH2

2A
1.0
-NH2

3A
2.0
-NH2

2.3 Characterization
2.3.1 Dynamic mechanical analysis
Dynamic tests, by dynamic mechanical analysis (DMA) on a Thermal
Instruments dynamic mechanical analyzer (Q800 TA), were also carried out in
three-point bending mode on specimens with dimensions of 12 x 2 x 60mm3.
Tests were performed with the amplitude of deformation during the bending of
25 m. The frequency-dependent storage modulus was also evaluated with a
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380 Materials Characterisation V


4.59 Hz frequency sweep at a constant temperature of 37C with 1.5% strain
and 0.01 N static force. Similar parameters were used by Hafeman and coworkers [11]. The storage modulus (E) value was recorded as a function of
frequency.
2.3.2 Abrasion resistance
The abrasion resistance of test samples was measured with a Schopper
Schlobach instrument with an APGi circulating roller from Heckert, and the
procedure complied with the standard PN-ISO [12]. The test pieces are in the
form of a roll (16 0.2 in diameter and 2mm high). Standard rubber from (The
Institute for Engineering of Polymer Materials and Dyes, Elastomer and Rubber
Technology Division in Piastw) was used as reference material [13]. The
abrasion resistance index (V) was calculated with the following relation:

Vs
, 100%
Vt

where Vs is the loss of volume of the standard rubber (mm3) and Vt is the loss of
volume of the test sample (mm3).
The density figures for the test pieces, which were necessary for calculations,
were found by the method described in the standard PN-ISO [14].
2.3.3 Atomic Force Microscopy (AFM)
AFM images were recorded at 37C in air using a Digital Instrument Multimode
Nanoscope V (Digital Instruments, Santa Barbara, CA) operating in the tapping
regime mode using antimony doped silicon cantilever tips (POL-15, 130 do
250kHz , 48 N/m). Scanner was used with scan rates between 0.5 and 1 Hz. All
images are subjected to a first-order plane-fitting procedure to compensate for
sample tilt. The microstructure of polyurethane was investigated on micro
sections. These were prepared using a rotary microtom RM 2165 (Leica) with a
LN 21 cooling device working at -60C.
2.3.4 Image analysis
Binary images revealing hard domains agglomerates were produced via digital
processing of AFM images. The size and volume fractions of the hard domains
agglomerates in polyurethane and nanocomposites were determined by
measurements on their sections [15]. Linear covariance method was used for the
description of the distribution of particles. The image was transferred to
MicroMeter software and quantitative analysis was performed. The diameters
were randomly determined on 5 microphotographs.
2.3.5 Fourier transform infrared (FTIR) spectroscopy
Infrared spectra of PURs were collected using a FTIR spectrophotometer
(Thermo Electron Corporation model Nicolet 6700). Measurements were carried
out using attenuated total reflectance (ATR) technique. Each sample was
scanned 64 times at a resolution of 4 cm-1 over the frequency range of 4000400
cm-1. Analysis of FTIR data enabled to determine the carbonyl hydrogenbonding index (R). A straight baseline was drawn in the spectrum between 1780
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Materials Characterisation V

381

cm-1 and 1640 cm-1 and the carbonyl stretching zone was corrected by
subtracting the baseline. To estimate the signal strengths, peak modeling of the
infrared active carbonyl bands was carried out using the Gaussian curve-fitting
method software OMNIC 7.3. The carbonyl absorption bands were deconvoluted
into component bands, the peak area of these bands was measured and carbonyl
hydrogen-bonding index R was calculated using Eq. (1) [16, 17]:

Abonded
A free

(1)

Moreover, the degree of phase separation (DPS) was obtained through Eq. (2):

DPS

R
R 1

(2)

3 Results and discussion


In polyurethanes application as short-term implants the modulus of elasticity and
surface properties must very often be changed. The one way to solve the problem
is the use of nanofiller [1820]. Nanocomposites exhibit advantageous
mechanical and physical properties already at small addition of modifying
particles, frequently lower than 5 wt%. Most of nanofillers occur without any
surface modification. However, sometimes we need to modify nanoparticles to
obtain better dispersion of nanofiller in polymer matrix, for instance. One of the
modifications is a chemical one relying on attaching functional groups i.e.
COOH, -NH2, -NCO, -OH to nanofiller [2024].
In this study were used polyetherourethanes with 0,52 wt% of nanosilica and
nanosilica modified with amino groups.
The change in elasticity module was examined in the course of three-point
bending as well as abrasion wear of fabricated materials (Table 2). Nanofiller
introduction change the storage modulus and abrasion wear of polyurethane
matrix.
Table 2:

Results of dynamic three point bending and abrasion wear of the PU


and PU/SiO2 composites.

Sample
E, storage modulus by frequency 5Hz at
37C, MPa
V, abrasion wear, dm3

24.6

2.8

32.6 30.8

1A

2A

3.4

40.6 41.6

3A

35.2 26.0 27.7 48.2 23.0 27.3 31.8

The introduction of 0.5 wt% of nanofiller brings about a decrease in storage


modulus and abrasion wear; bigger amounts of the filler make the two values
grow. The use of modified nanofiller results in the fact that the obtained
nanocomposites have a higher storage modulus at lower abrasion wear.
In order to explain the mechanism of the influence of nanofiller on
polyurethane matrix structure microscopic observations were carried out of the
cross-section surface of fabricated materials using AFM. An AFM tapping mode
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382 Materials Characterisation V


is used to depict topographic features and the spatial variation in surface by
height and phase imaging. For the examined materials the appearances of
topographic and phase images are similar and show less obviously surface
morphology related to hard domain and soft domain separation. An exemplary
phase image of surface cross-section of examined PU is shown in Fig. 2a. Binary
images of all face images of the polyurethanes and nanocomposites were
performed and those selected from them were shown in Fig. 2 (b-f). The neat
PU cut surface showed microphase separation in phase images, the hard phase of
the polyurethane appears brighter than the soft phase. The hard phase during
phase separation formed island domain like phase. The results in all
nanocomposites are similar, showing a distinct topology of phase separation of
hard and soft segments (Fig 2b-f). Images of Pu phase structure and
nanocomposites are similar to the images obtained by Zhang et al. [21].
The AFM images could be explained as follows: Glycerine reacted with MDI
and then formed island domain like hard phase. This usually accompanied
chemical reactions such as cross-link, so the segments shrank as a result [22] and
formed caves like those in PU and nanocomposites.
The introduction of 0.5 wt% unmodified filler (Fig. 2c) makes the appearance
of smaller islands, formed by hard phase, than in PU (Fig. 2b), visible in the
pictures of cross-section surfaces of the nanocomposites. The use of 0.5 wt.%
SiO2 modified by NH2 groups results in the growth of the size of islands formed
by hard phase; moreover, they tend to merge into bigger agglomerates (Fig. 2d).
The size of the agglomerates of the hard domains was increased respectively
to the nanofiller contents as shown in Fig. 2e and f c.
Nanda and his co-workers have reported small amounts of POSS usually
tending to combine with hard segments and affect the properties of the hard
segments of PU [23]. Changes in the morphology of polyurethanes, caused by
the introduction of POSS, were also observed by Zhang and co workers [24]. It
can be assumed that the mechanisms of changes caused by the use of nanosilica
are similar. Quantitative analysis of binary pictures was used for the description
of morphology of PU hard phase and its nanocomposites. Since hard phase
created islands, often merging into bigger agglomerates, the agglomerates
volume formed by hard phase was calculated and the results are presented in
Fig. 3
The difference in the level of interaction by hydrogen bond between the hard
segments of the materials can regarded as an explanation of the differences in the
volume of the agglomerates created by hard phase of the examined materials;
hence the determination of hydrogen bond index (R) and phase separation index
(DPS). The said difference in the level of interaction was determined basing on
the vibrations of carbonyl groups occurring within the scope of wavenumbers
1760-1680cm-1. The comparison of spectra in this scope for materials with equal
nanosilica content modified with NH2 groups is shown in Fig. 4.

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Materials Characterisation V

a)

Figure 2:

383

b)

c)

d)

e)

f)

AFM phase images at 5 m scan sizes of (a) sample 0 and binary


images: (b) sample 0 (c) sample 1 (d) sample 1A (e) sample 3 (f)
sample 3A. Z ranges: 30.

The R and DPS values of the polyurethane/nanosilica nanocomposites


mixtures are given in Table 3. After the introduction of 0.5 wt.% of nanosilica,
the R and DPS is higher than for polyurethane but modification causes a
decrease in R and DPS. When a bigger amount of nanosilica is applied then R
and DPS increase by adding NH2 group on the surface of nanosilica.
Several factors influence the DPS of polyurethane such as molecular weight,
segmental length, crystallizability of soft segments, overall composition and
intra- and inter-segments interactions [2527]. The addition 0.5 wt% nanosilica
causes weakening of the hydrogen-bond interactions created between
polyurethane hard segments; segmental incompatibility in the polyurethane
decreases by adding nanosilicas (Table 3). This explains the formation of the
structure visible in the cross-section of the materials (Fig 2c, d). After the
introduction of a bigger amount of the filler we observe no weakening of
hydrogen-bond interactions created between polyurethane hard segments. A
bigger amount of the filler increases incompatibility in the polyurethanes,
causing a higher degree of phase separation in the polyurethane (Table 3).
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384 Materials Characterisation V


80
70
60
Vv, %

50
1.

40

2.

30
20
10
0
0

0,5

1,5

2,5

SiO2 content, wt %

Figure 3:

Influence of nanosilica content on volume fraction of hard domains


agglomerates in PUR: (1) nanosilica, (2) modified nanosilica.

Figure 4:

Influence of modified nanosilica content on FTIR spectrum in the


range 17601680 cm-1.
Table 3: Parameters of polyurethane phase separations.

Sample
R
DPS

0
0.079
0.073

1
0.041
0.040

2
0.069
0.064

3
0.090
0.082

1A
0.071
0.,066

2A
0.105
0.095

3A
0.109
0.099

Moreover, in surface cross-sections of the examined nanocomposites bigger


agglomerates of hard domains can be seen (Fig. 2e and f). Most probably, the
increase in the degree of phase separation of this nanocomposites group can be
attributed to the growth of the chain mobility in the polyurethane allowing the
creation of more ordered phases, with respect to the polyurethane without
nanosilica. A smaller amount of nanosilica weakened the interactions between
hard segments but caused no growth of the chain mobility; it was only after
adding bigger amounts of nanofiller (above 1%) that an increase in
nanocomposites chain mobility was observed. Surface modification of nanosilica
by NH2 groups results in the increase in phase separation (Table 3), the volume
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Materials Characterisation V

385

of hard domain agglomerates increases (Fig. 2d and f), which is the result of
reaction of NH2 groups on nanosilica surface and NCO groups in hard segments.
This reaction weakens chain mobility and creates favourable conditions for phase
separation in this nanocomposite group.

4 Conclusion
Within the framework of the work the influence of the quantity and modification
of nanosilica on the properties of polyurethanes was assessed; the polyurethanes
are intended to be used as short-term implants exposed to abrasion wear. The
addition of 0.5wt% of nanosilica caused a decrease in storage modulus and
abrasion wear of nanocomposites. Bigger amounts of nanosilica result in a
significant growth of storage modulus. The modification of nanosilica surface
with NH2 groups adds to the increase in the modulus and to a favourable fall in
the abrasion wear of the examined nanocomposites.
The joined qualitative and quantitative analysis of AFM pictures of
polyurethane structure and its nanocomposites as well as the analysis of phase
separation degree, performed on the basis of FTIR spectra, permitted to explain
the causes of changes in the properties brought about by the introduction of
nanofillers.

Acknowledgements
The authors are grateful to the Warsaw University of Technology for financial
support of this study. Thanks are also offered to Dr Maria Zielecka from the
Institute of Industrial Chemistry for the carrying out of nanosilica modifications.

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Ajayan P.M., Schadler, Braun P.V. Nanocomposites Science and
Technology, Wiley-VCH Verlag, Weinheim, 2003.
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Bliznyuk, V. N.; Tereshchenko, T. A.; Gumenna, M. A.; Tomza Y. P.;
Shevchuk, A. V.; Klimenko, N. S.; Shevchenko, V. V. Polymer 2008,
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Macromolecules 2006, 39, 7037.
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20:70712.
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Materials Characterisation V

387

Description methods of the properties of


composites from oxybiodegradable
foil waste and wood
J. Ryszkowska & K. Saasiska
Warsaw University of Technology, Faculty of Materials Science and
Engineering, Poland

Abstract
As part of this work oxydegradable polymer was fabricated and analyzed; it was
made from the waste following a 30 day exposure in Xenotest, simulating a
2-year exposure in atmospheric conditions and undergoing a triple injection
process. Similar examination was applied to composites containing 32 wt.% of
wood fabricated from this polymer. In the course of the examinations two
methods of degradation process evaluation of the materials were verified. It was
stated that the method utilizing the relationship between peak fields originating
from scissoring vibrations of the (-CH2-) group with a frequency of ca 1463cm-1
ensures more accurate results. The results of other examinations of the two
groups of materials permit us to state that the manufacturing of composites with
wood constitutes an interesting form of the utilization of oxybiodegradable
polymers.
Keywords: oxydegradable polyethylene, foil waste, recycling, wood.

1 Introduction
According to the data by Plastics Europe, European association of plastics
manufacturers, some 230 million tons of plastics were produced in 2009 in the
world (55 million tons in Europe). About 50% of the materials constitute
polymers intended for the packaging industry, of which 40% are polyolefines:
polyethylene (PE-LD, PE-HD, PE-LLD) and polypropylene (PP).
These polymers are made from petroleum-based synthetic polymers that do
not degrade in a landfill or in a compost-like environment. However, increased
use of synthetic packaging films has led to serious ecological problems. Several
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388 Materials Characterisation V


approaches to solve the pollution problems caused by polyolefines were
developed in the 1970s [1]. One of the solutions was the introduction of prooxidants to the polymers. The pro-oxidants Co, Mn, Cr, Ni, Mo and Fe on Al2O3
or SiO2 support [26], cause that polymers become susceptible to environmental
effect. Polyolefines prepared in this way are called oxo-biodegradable.
Degradation of all polymers follows a sequence in which they are converted
into their single oligomeric or monomeric units and later they are utilized as
carbon source by the microbes. Lower molecular weight hydrocarbons are more
susceptible to attack by microorganisms than the high molecular weight polymer.
The degradation of polyolefines with pro-oxidants addition proceeds in a similar
way [718].
The presence of pro-oxidants, particularly, provided superior functionality
and higher degradation rate in PE films. Though their degradation time varies
between 18 and several dozen months, they often land up at the rubbish dump
after a month of use. Within the framework of the works a selective collection of
this type of waste was proposed along with the production of composites with
wood, fabricated from them. Such composites can be used in various fields, i.e.
as elements for seasonal gardening, auxiliary materials for agriculture, urban
greenery, etc. Later on they can serve as valuable energy raw materials.
One of the problems connected with the utilization of products made from
such composites is the assessment of their exploitation time.
The assessment of the usefulness of climatically hazard materials is carried
out by Xenotest type of equipment [15]. After the exposure in such equipment
various properties of polymer materials are examined including, first of all,
mechanical properties and thermal analysis. However, since the availability of
Xenotests is rather limited, other methods are sought after.
In the current study an attempt has been made to understand the degradation
of composites from waste polyolefines with pro-oxidant and wood. The changes
in the various physiochemical properties of the polymer were monitored to
elucidate the degradation process. As part of work and in order to assess the
oxidation process occurring during the degradation of oxydegradable polymers
and their composites, methods were verified utilizing spectra obtained with the
use of infrared spectroscopy.

2 Experimental
2.1 Materials
Production waste, degradable polyethylene HDPE, containing 1 wt.% of prooxidant d2w, from Ecoplastic Poland, (OXY) was a kind of gift from Ecoplastic
Poland. Wood fibers Lignocel C 120 with particle size 70 150 m, from
J. Rettenmaier & Shne GmbH, Germany.

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Materials Characterisation V

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2.2 Sampling
Composite samples were fabricated in two stages. In the first stage, with the use
of T-45-25-22T-VS single-screw extruder with screw ratio L/D= 29 and with the
head for granulation able to simultaneously extrude six 5mm profiles, a granulate
was extruded containing 25 wt.% of wood flour. The extrusion process was
conducted at the temperatures of 150/160/170/175/175C (starting from the
charging hopper). After cooling the extruded rods were ground using a mill for
plastics. In the second stage wood flour was added to the granulate obtained
from the mixture in such quantity so that its total content in the composite should
reach 32% mass; next, the granulate of composite mixture (or oxybiodegradable
polymer) was placed in the bunker of DrBoy 22A injection moulding machine.
The regranulate and wood fibers as well as the obtained granulates were then
dried before each processing stage in DAC6 dryer at 80C for one hour. During
the injection of samples the cylinders temperature, starting from the bunker,
amounted to 155, 160, 170, 178 and 180C, injection pressure 800 105 Pa, and
clamp pressure of 800 105 Pa. Injection time was ca 2 s, clamp time 12 s,
cooling time 8 s; the total cycle time equaled ca 25 s. From all types of materials
samples A1 were fabricated in conformity with the norm EN ISO 527-2 using a
2-cavity mould cooled with water at 40C.
In order to verify the influence of injection process on the degradation process
of oxydegradable polymers and their composites a 3-time injection process was
carried out. Samples obtained in the first injection cycle were ground in an
industrial mill, dried and injected. This cycle was performed twice. A description
of the achieved materials is presented in Table 1.
Table 1:

Description of the achieved materials.

Sample
1
2
3
1.32 2.32 3.32
Composites matrix
OXY OXY OXY OXY OXY OXY
Amount of wood
32
32
32
[wt.%]
Process multiplicity
1
2
3
1
2
3
2.3 Characterization
Resistance of the materials to accelerated ageing was determined on the basis of
analysis of pictures taken with the use of microscopic scanning, Charpy impact
tests as well as FTIR analysis of samples after irradiation. The examination was
carried out in conformity with PN-EN ISO 4892-1, PN-EN ISO 4892-2 and PNEN ISO 20105-A02:1996.
The samples underwent exposure in Xenotest Alpha High Energy equipped
with xenon lamp as radiation source. The examination was carried out for 720h
with samples being subjected to irradiation of 388,8MJ/m2 (within the scope of
300-400nm) equivalent to a 2-year exposure in natural conditions [19]. The
exposure in Xenotest is shown in Table 2.

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390 Materials Characterisation V


Table 2:

Ageing test parameters in Xenotest alpha HE.

Parameter
Filter
Luminous intensity E, W/m2
Work mode
Temperature control
Temperature in chamber C
Rain
Relative humidity, %
Phase time, min

Phase 1
Phase 2
Xenochrome 300
1503
1503
without
without revolution
revolution
in chamber
in chamber
353
303
no
yes
rain
503
102
18

SEM picture from the surface of examined samples dusted with gold was
achieved using an electronic scanning microscope Hitachi S-2600 with
accelerating voltage of 10 kV.
Infrared spectra of PURs were collected using a FTIR spectrophotometer
(Thermo Electron Corporation model Nicolet 6700). Measurements were carried
out using attenuated total reflectance (ATR) technique. Each sample was
scanned 64 times at a resolution of 4 cm-1 over the frequency range of 4000400
cm-1. Analysis of FTIR data enabled to determine the carbonyl index.
Charpy impact resistance using Resil 5,5 hammer by Ceast, wg PN-EN ISO 1792:2001 was defined for samples with notch, size 70 4 10 mm (cut from
samples and formed via injection).
Mechanical properties at static stretching in conformity with PN-EN ISO 5271:1998 and PN-EN ISO 527-2:1998 were examined using the strength machine
MTS Q/Test 10. Five 1A samples were analyzed from each type of composite.
The samples were stretched at the speed of 10 mm/min. The measurements were
recorded automatically using programme TestXpertII. Determined values:
strength in the area of plasticity (), strain at break ( ) and Young elasticity
modulus (E) of polymers and composites.
Absorption after water soaking was determined basing on the change in the
mass of 3 randomly selected samples from a given part of the material. The
examination was carried out in conformity with the technology specified in the
norm PN-EN 317:1999.

3 Results and discussion


In the course of conducted examinations the samples from oxybiodegradable
polymer and its composite, fabricated via single injection process, were
subjected to exposure in Xenotest. In result of the exposure, simulating a 2-year
ageing process in natural conditions a degradation of the examined
oxybiodegradable polymers took place (Fig. 1). The degradation was visible in
the form of white ovals appearing on a sample not directly subjected to UV
radiation (Fig. 1a) as well as in the form of cracking on the surface of a sample
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Materials Characterisation V

391

directly subjected to action of the xenon lamp (Fig. 1b). No such visible changes
were observed on the surface of composites (Fig. 2). Degradation of polymers
and composites results in the decrease in their impact resistance (Table 3).

Figure 1:

SEM pictures of the surface of oxybiodegradable polymer after 30


days ageing in Xenotest: surface not exposed to a direct radiation of
xenon lamp (a), subjected to a direct radiation of xenon lamp (b).

Figure 2:

Rys. 2. SEM pictures of the surface of oxybiodegradable polymer


with 32 wt.% of wood, not exposed to a direct radiation of xenon
lamp (a), after 30 days ageing in Xenotest (b).

Table 3:

The change in impact resistance of oxybiodegradable polymers and


composites containing 32 wt.% of wood, caused by 30 days
exposure in Xenotest. 1 sample of oxybiodegradable polymer, 1.32
sample of its composite, 1D and 1.32D samples after exposure in
Xenotest.
Sample
U, impact resistance, kJ/m2

1 1.32 1.D 1.32D


43.9 9.7 33.6 9.6

In oxybiodegradable polymer the impact resistance after exposure in Xenotest


decreased by ca 23% while that of the composite only by ca 1%. In order to
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392 Materials Characterisation V


assess changes in the structure of polymer and composite, causing the decrease
in impact resistance after exposure in Xenotest a spectroscopic analysis (FTIR
ATR) of them was carried out. The achieved spectra of polymer and composite
are shown in Fig. 3.

Figure 3:

FTIR-ATR spectra of oxybiodegradable polymer samples before (1)


and after exposure in Xenotest (1D) and composites before (1.32)
and after exposure in Xenotest (1.32D).

Basing on FTIR ATR spectra carbonyl index (COI) was calculated by two
methods. In the first one, proposed by Reddy and co-authors [16] and Corti et al.
[14], carbonyl index was determined as the ratio of absorbance of band 1716
cm-1 resulting from the vibrations of (C=O) carbonyl group and absorbance of
band 1468 cm-1 originating from scissoring vibrations of group (-CH2-).

COI

A1716
A1468

(1)

In the second method, proposed by Douminge and co-workers [18] and Stark
and co-workers [15] carbonyl index was determined as the ratio of absorbance
of band 1716 cm-1, resulting from the vibrations of (C=O) carbonyl group and
absorbance of band 2913cm-1, originating from the asymmetric stretching
vibrations of group (-CH2-).

COI

A1716
A2913

(2)

The fields of individual bands were determined with the use of OMNIC 7.3
programme. The analysis was carried out after correction of baseline, the
spectrum in the analyzed scope was resolved into component bands using the
Gaussian curve-fitting.

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Materials Characterisation V

Table 4:

393

Calculation results of carbonyl index.

Sample
COI calculated acc. to formula (1)
COI calculated acc. to formula (2)

1
0.015
0.005

1.32
0.068
0.019

1.D
0.019
0.006

1.32D
0.041
0.012

In the results of the calculation of carbonyl index using the first method it was
stated that the index is three times higher than that calculated by the second
method according to formula (2) (Table 4). Therefore, it was agreed that the first
method will ensure a more accurate analysis of degradation changes in
oxybiodegradable polymers and composites with wood, fabricated from them.
To verify this statement an analysis was performed of carbonyl index of the
polymer and composite containing 32 wt.% of wood nanofiller after multiple
processing and using the first method (Table 5). Carbonyl index is used to
monitor the progress of oxidation process. An increase in COI was observed in
oxybiodegradable polymers and composites, which indicates that degradation
process in these materials occurs after each processing cycle. After consecutive
stages of processing the speed of COI changes in composite with wood
decreases, which means that the introduction of wood slows down the
degradation process. Also examined were the strength properties, impact
resistance and water absorption of the materials; the results are shown in Table 5.
Table 5:

Examination results of oxybiodegradable polymer and composites


with 32 wt.% of wood and after multiple injection process.

Sample
COI calculated acc. to formula
(1)
U, impact resistance, kJ/m2
A, humidity content, %
E, elasticity modulus, MPa
, stress in the area of plasticity,
MPa
, strain at break, %

1
0.02

1.32
2
0.03 0.09

2.32
0.06

3
3.32
0.23 0.07

38.5
0.02
820
152

8.0
3.48
1740
19

36.7
0.02
210
105

9.0
3,43
410
26

31,2 11.0
0.08 3,12
205 390
80
27

450

4.4

280

4.9

120

5.7

The examination results of strength properties confirm that after consecutive


processing cycles the degradation process of composites proceeds more slowly
than the degradation process of matrix polymers. Also, after consecutive
processing cycles water absorbency of the composites favourably decreases.

4 Conclusion
Within the framework of the work a possibility of manufacturing practical
materials from oxybiodegradable polymers waste was assessed as well as their
composites with wood flour filler. The possibility of utilizing recycled
oxybiodegradable polymers requires the assessment of their degradation degree
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394 Materials Characterisation V


prior to processing. To this end the use of carbonyl index is proposed. Two
methods of its determination were verified. It was stated that the method utilizing
the ratio of peak field originating from scissoring vibrations of group.
(-CH2-) ensures more accurate results. This method was used for the
assessment of degradation degree of oxybiodegradable polymers and their
composites subjected to the exposure in Xenotest, simulating a 2-year exposure
period in atmospheric conditions and following a three-time injection process.
Apart from degradation itself, selected properties of the materials were also
evaluated. In result of the examinations it was stated that each processing course
accelerates the degradation process of oxybiodegradable polymers. The
introduction of wood affects the degradation process of the matrix. Further
processing causes smaller changes in the properties of composites than in
polymers.
The results show that oxybiodegradable polymer waste, not often utilized so
far, may constitute a valuable raw material for manufacturing practical products.

Acknowledgements
The study has been financed by the National Research and Development Centre
within the framework of the project N R15 0023 06 / 2009, titled: Polymer
Composites with Biomass
The examinations in Xenotest were carried out by a team headed by Prof.
Ph.D. Eng. K. Czaja at the faculty of Chemistry, Opole University, Poland.

References
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[6] Wiles DM, Scott G. Polyolefins with controlled environmental
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[7] Chiellini E, Corti A, Swift G. Biodegradation of thermally-oxidized,
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[8] Hasan F, Shah AA, Hameed A, Ahmed S. Synergistic effect of photo and
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[9] Albertsson A-C, Andersson SO, Karlsson S. The mechanism of
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[10] Albertsson A-C, Karlsson S. Three stages in degradation of polymers
polyethylene as a model substance. J Appl Polym Sci 1988; 35:1289302.
[11] Albertsson A-C, Barenstedt C, Karlsson S. Susceptibility of enhanced
environmentally degradable polyethylene to thermal and photo-oxidation.
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[12] Sipinen AJ, Rutherford DR. A study of the oxidative degradation of
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[13] Hakkarainen M, Albertsson A-C. Environmental degradation of
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[14] Corti A., Muniyasamy S., Vitali M., Syed H. Imam S.H., Chiellini E.
Oxidation and biodegradation of polyethylene films containing pro-oxidant
additives: Synergistic effects of sunlight exposure, thermal aging and
fungal biodegradation, Polym Degrad Stab 95(2010) 1106-1116.
[15] Stark N.M., Laurent M. Matuana L.M., Surface chemistry changes of
weathered HDPE/wood-flour composites studied by XPS and FTIR
spectroscopy, Polymer Degradation and Stability 86 (2004) 19.
[16] Reddy M.M., Deighton M., Gupta R.K., Bhattacharya S.N., Parthasarathy
R., Biodegradation of Oxo-Biodegradable Polyethylene, J Appl. Polym Sci,
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[17] Jakubowicz I., Narahmadi N., Petersen H., Evaluation of the rate of abiotic
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[18] Douminge L., Mallarino S., Cohendoz S., Feaugas X., Bernard J., Extrinsic
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Materials Characterisation V

397

The effect of slag composition on recycling of


OFHC through the ESCM process
S. Ketabchi, F. K. Ahadi, K. Hanaee & S. H. Alhoseini
Academic Center of Education, Culture and Research, Tehran, Iran

Abstract
This paper reports the results of an investigation into the role of the slag
composition in recycling Oxygen Free High Conductivity (OFHC) copper
through a modified Electroslag Remelting Process (ESR) melting technique
Electroslag Crucible Melting (ESCM). Materials used for the slag were alumina
(Al2O3), cryolite (Na3AlF6), sodium fluoride (NaF), and fluorine (CaF2) at
different ratios. The results showed that in addition to purity of the slag and
graphite used in the electrode and crucible, the percentage of alumina component
in the slag composition was the main factor in the attainment of the purity. The
best consequence was achieved when the content of alumina was in the range of
2327%. Furthermore, in ternary compound systems with constant one
component, the influence of the weight ratio of the other components was
investigated, from a product purity viewpoint. Finally, in the optimized
condition, copper with 99.988% purity was achieved, yielding an electrical
conductivity of 100.1% IACS.
Keywords: OFHC copper, recycling processes, electro slag remelting, ESCM
process

1 Introduction
Recent developments in electronic industries and energy fields have pushed the
property requirements for oxygen free copper to the extreme. When recycling the
OFHC copper, the main problem is to reduce oxygen contamination because it
not only impairs the conductivity but also the mechanical properties of the
material, possibly leading to high scrap losses [14]. Oxygen free copper is used
in applications where the parts are going to be annealed in a hydrogen containing

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398 Materials Characterisation V


atmosphere. The presence of oxygen in either it's elemental state or as copper
oxide, leads to the formation of water vapor, which means the brittleness of the
material [5].
Two major techniques are used to reduce the oxygen content in copper. The
first one involves casting in an inert atmosphere and fluxing the molten copper
with an inert gas to prevent the oxygen involvement. The other approach which
is a deoxidizing method consists of adding a reductive material to the melt to
form selective oxide (instead of copper oxide). The reactive material must be
chosen so that its oxide is stable and could not be reduced by hydrogen during
annealing. Unfortunately, most of the reductive materials have highly deleterious
effects on electrical conductivity if remain in the solid solution of copper.
Because of the nature of these oxidants, it is difficult to accurately control the
amount of reactive materials. So it's confronted with diminishing of conductivity.
In conventional methods of producing OFHC copper, clean cathodes are melted
in contact with carbon in an electrical furnace under a protected atmosphere or in
vacuum. The protected atmosphere is a mixture of carbon monoxide and
nitrogen gases [3, 611]. After charging clean cathodes in an induction melting
furnace, providing the necessary vacuum or protected environment, the oxide
removal agent is added to the completed melt without any intermission.
In this technique, the amount of this agent must be calculated as precisely as
possible. It must first react with all the oxygen available in the composition and
bring it into the slag and secondly, no residue of it remains as impurity in the
melt [8].
Researches on the effect of vacuum on the other elements, also shows that Sb,
As, and Bi reduces up to 90% and large fraction of S is removed as sulfur
dioxides [8, 12]. Nesslage et al. produced OFHC copper with an electrical
conductivity of 101% IACS just by adding approximately 30 ppm manganese
[13]. Yurko and Peckens used a method to produce oxygen free copper from
copper powders. The powders produced by hydrogen reduction from an aqueous
ammoniac solution was formed into briquettes by cold compression and then
heated in AC confined area at temperature of 1750F for 1 h under reducing
atmosphere of oxygen [14].
It is evident that, OFHC copper is nearly a precious material; therefore,
recycling of the shavings produced in manufacturing processes is an interesting
object. Because of a high surface to volume ratio of this kind of scraps, melting
them in vacuum furnace is not possible and if so, it is not an economic solution.
Consequently, they can not be recycled by ordinary techniques.
ESR or electroslag remelting is a process used for remelting and refining of
special alloys which are used for critical applications in aircraft, thermal and
nuclear power plants, defense hardware, etc. The principal set up of an
electroslag remelting plant is shown in Figure 1. An electroslag remelting
process (ESR) starts when the lower tip of a consumable electrode is immersed
into a pool of molten slag. The pre-melted slag possessing electrical conductivity
is located on the water-cooled mold base connected to a power supply. The
electric current (commonly AC) passing through the slag keeps it at high
temperature, which is about 360F (200C) higher than the melting point of the
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Materials Characterisation V

399

metallic electrode. The electrode tip is heated by the hot slag and starts to melt
forming droplets of liquid metal, which disconnect from the electrode and sink
through the slag layer.

Figure 1:

Schematic illustration of Electroslag Remelting (ESR) operation.

The ESCM (Electro Slag Crucible Melting) method was first invented by
Borodin and co-workers in 1985 with inspiration from the ESR process [6, 16].
The main target was to design a system for remelting the scraps. The results of
analysis showed the fact that applying this method results in decreasing the
amount of Sn, Pb and S; although the Fe and Zn content may increase due to the
contamination of the charged scraps [2, 16]. The produced ingots are free of
impurities, voids, shrinkage and gas porosities. In addition, the problem of
hydrogen embrittlement due to annealing (at high temperatures about 400C) is
reduced substantially [6, 16].
In ESCM method, the consumable electrode in ESR (made of the charge
material) is replaced by a non-consumable graphite bar and a water-cooled
copper mold is superseded by a graphite one. Schematic illustration of ESCM
process is shown in Figure (2). This collection is set on a water-cooled base
plate. Scrap is fed in small pieces after complete melting of the slag. These
shavings are melted through passing the slag and form melt pool behind it.
Finally, the molten metal covered by slag is cast into a permanent graphite
mould [2].
Use of graphitic crucible and electrode makes it possible to reduce the oxygen
content of the melt remarkably. In addition, the high deoxidizing capacity of
graphite ceases the addition of deoxidizing agent, e.g. Lithium, copper phosphor,
etc. which usually decrease the electrical conductivity of copper. Besides, for the
reason of the very low solubility of carbon in copper (about 0.0025% in
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400 Materials Characterisation V

Figure 2:

Schematic illustration of Electroslag Crucible Melting (ESCM)


process.

25C temperature), it can be used without the problem of carbon dissolution [6].
This method has several advantages such as simplicity of the equipment, the
lower cost and possibility of recycling scraps of OFHC copper besides nearly
uniform mechanical properties such as toughness in all directions [2, 6]. The
results of Prasad et al. experiments have shown that while using cryolite, the
content of oxygen decreases considerably. However, the harmful impurities such
as Si, Fe, and S attract into the melt to a substantial extent so the melt doesn't
have sufficient purity in this respect [17]. Therefore, in this research, it would be
attempted to reduce the amount of impurity elements especially Fe and Si via
altering slag composition. For this purpose, cryolite was replaced by mixtures of
sodium fluoride and alumina, two effective components in preventing oxygen
pick-up, with different ratios. An adequate fluidity of the slag as well as its
ability of providing the desired temperature was considered in determining the
slag composition.
1.1 Experimental procedure
An AC ESCM system with a capacity of 150 KVA, comprising a graphite
electrode of 50 mm diameter and a graphite crucible with internal diameter of
105 mm was used to do the tests. Copper scrap was in the form of pieces with 5
mm diameters and the lengths of 2-3 cm. These particles were dipped in a 10%
HCl solution for 20 min to remove the surface oxides and then dried in the air.
The slag combination consisted of alumina, fluorine, cryolite and sodium
fluoride in various ratios. The compositions are listed in table 1.
It can be seen from the table 1 that, various NaF to Al2O3 and CaF2 to Al2O3
ratios were investigated in constant CaF2 and NaF respectively. The effect of
slag recycling was also studied by reusing a certain slag in the next melting. 4 kg
of copper scrap and 2 kg of slag were used for each experiment. The slag
materials were preheated in a resistance furnace up to 600C for 2.5 h. The
process started with an arc between the graphite crucible and the electrode.

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Materials Characterisation V

401

Table 1: Chemical composition of the slag used in various testing conditions.


Sample No.

CaF2 (%)

Al2O3 (%)

Na3AlF6 (%)

NaF (%)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

10.5
30
30
30
40
10.5
30
30
30
23
35
40
33
35
35
37

4.5
40
35
30
15
4.5
12.5
40
35
30
17
20
15
27
15
25
23

85
15
85

30
35
40
30
-

in addition to the recycled slag of test No 6

25
-

30
35
40
60
45
45
40
25
40
40

Once the arc was stabilized, the slag was charged into the crucible. The heat
required for the process was generated due to Ohmic resistance of the slag pool
by the passage of electric current through it. When the slag was completely
melted, the copper pieces were gradually added to the molten slag and melted.
The molten slag covered the liquid copper and protected it from atmospheric
contamination during the process. The slag composition was selected properly,
so, passing the charge through, the oxide particles could be entrapped and the
clean liquid metal was collected at the bottom of the crucible. During crucible
melting, the melt and slag temperatures were measured using a thermometer. The
temperature of the melt was maintained constant at about 1500C by changing
the voltage of the power supply and/or changing the distance between the
electrode and the crucible bottom. After the copper was completely melted, the
power was kept constant at about 28 KV for 7 min in order to complete the
chemical reactions. Chemical analysis of the ingots was determined using an
analyzer, and the oxygen content was also specified by LECO (ASTM B 170).
The electrical conductivity was measured for some of the specimens by Ely
chemical plant (DIN 48200, 48201). Tensile tests were performed by a MTS
machine according to ASTM E 8M standard (D = 2.5 mm) and microstructural
observations were carried out after preparation of the samples, polishing, and
etching by a potassium dichromate solution for 10 sec.

2 Results
Chemical analysis of the primary OFHC scrap is presented in Table 2.
Table 3 shows the effect of the slag composition on the final analysis. The
amount of oxygen content and electrical conductivity for some of the samples
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402 Materials Characterisation V


was recorded. In all the samples, higher contents of impurity elements such as Si,
Fe and P were observed as compared with the former analysis due to pick up
from slag.
Table 2:

Chemical analysis of primary OFHC copper (ppm).

Fe S
Te
As Se Sb Cd Cr Pb Si Bi
Ag Zn Ni Co Mn Sn
<1 6.5 <1.2 <1 0.5 <1 3.5 <1 3.5 <1 <0.6 8.6 <3 1 <2 0.34 <1

Table 3: Amounts of different elements of impurity (ppm), the purity of Cu and


the electrical conductivity for various testing conditions.

Sample
No.

Fe

Si

Al

Other

1
2
3
4
5

2900
500
1500
200
360

2500
2500
2800
1700
730

260
110
30
20
20

750
1300
50
790
<1

700
1700
1000
100
360

15
-

230

320

30

<1

450

40

230

10

<1

<1

330

410

70

<1

700

290

420

30

<1

450

10

200

300

20

<1

100

11

200

570

10

<1

40

12
13

140
40

150
80

50
20

<1
<1

90
400

47

14

30

30

<1

130

42

15
16
17

11
10
32.6

101
78
<1

29.4
27.3
35.9

<1
<1
<1

10
-

33
12
18

Mn=40
Mg=700
Mn=40
Mg=800
Pb=230
Pb=60
Zn=240
Pb=60
Sn=40
Pb=50
Sn=20
Zn=40
Pb=60
Mn=20
Pb=60
Sn=20
Zn=80
Mn=20
Pb=40
Mn=10
Pb=30
-

Cu
purity
99.200
99.150
99.390
99.550
99.680

Conductivity

99.850
99.920

99.90

89.6

99.950
99.940

91.7
95.9

99.980

100

99.974
99.985
99.988

96.1
100
100.1

As it is shown in Figure 3, it can be inferred from the comparison of samples


8 to 11 that the addition of NaF to Al2O3 weight ratio at constant CaF2 percent
results in a higher purity of the produced copper (Figure 3). Also, comparing
samples 15 to 17 shows that increase of CaF2 to Al2O3 weight ratio at constant
NaF percent leads to production of higher purity ingot (Figure 4). It was reported
that recycling of slag containing alumina resulted in diminishing pick up of
oxygen [17]. Comparison of samples 6 and 7 shows that recycling of slag results
in lower pick up of Fe, Si, S and Al into the copper ingots and therefore, the
purity of the ingot is increased. The reason is attributed to the impurities that
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Materials Characterisation V

403

transferred from the slag into the first melt and then the recycled slag is of lower
contamination. Samples 8, 9 and 10 have the same production parameters as
samples 2, 3 and 4 respectively, but the higher purity of graphite used for
crucible and electrode; that leads to the higher purity of the final product.

Figure 3:

Influence of increase in the NaF to Al2O3 weight ratio in the slag on


purity of the copper.

Figure 4:

Influence of increasing the CaF2 to Al2O3 weight ratio in the slag


on purity of the copper.

3 Discussion
The aim of this research is the assessment of the capability of ESCM process in
recycling of precious OFHC scrap with acceptable product purity. Introduction
of oxygen into the melt leads to take place the oxide compounds. Since these
kinds of inclusions have fragile natures, the presence of such particles in the
microstructure, particularly on the grain boundaries results in lessening the
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404 Materials Characterisation V


workability of the ingot. In addition, from the electrical conductivity point of
view, it's necessary to avoid entering of any impurity in the melt. Microstructures
of the sample no. 17, one having the highest purity in this work, are shown in
figure 5. As can be seen, the grains and grain boundaries are thoroughly free of
either oxides particles or other kinds of inclusions.
Besides, due to settlement of hot graphite crucible over the water-cooled
copper base plate, directional heat flow exists during the solidification process.
Furthermore, a thin slag skin is formed around the casting inside the mold and
hot slag solidifies above the ingot which protects it from atmospheric
contamination. Based on this reason, sound ingots without any shrinkage cavity
or the other defects could be obtained in "ESCM" process.
It was also observed that, one of the most principal factors in ESCM process
affecting on the product purity is the purity of the materials with which the
molten copper is in contact (electrodes, crucible and slag components). The
major impurities to be considered are iron, silicon, sulfur and oxygen. Entrance
of iron to the melt was attributed to the reduction of iron oxide by graphite
electrode or crucible by Prasad et al. [17]. In this research, it was also observed
that iron content decreases in ingots using recycled slag of the other melts
(Table 3, melt No. 7).

Figure 5:

Microstructure of sample No. 17.

Also, increasing silicon and sulfur content in the melt can be attributed to
reduction of their oxides in slag composition. These compositions are introduced
via fluorine and sodium fluoride [17].
Previous researches have mentioned oxygen content reduction using cryolite
as a slag component, but the results of this study determined that it's
accompanied by silicon, iron and sulfur increase in the melt. As Table 3
represents, the best slag composition (40% sodium fluoride, 23% alumina, 37%
fluorine) results in a product with a purity of 99.988% and electrical
conductivity of 100.1% IACS.

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Materials Characterisation V

405

4 Conclusions
1.
2.

3.
4.
5.
6.
7.

ESCM is a successful and practical process for recycling of OFHC copper


scrap.
Considering the results shown in figs 2 and 3, this shows that in these
experiments the best results were achieved when the content of alumina in
the slag is in the range of about 23-27%.
Using graphite with high purity in electrode and crucible has a very
important role in obtaining higher quality product.
In ternary compound systems with constant NaF percent, when the weight
ratio of CaF2 to A12O3 increases, the product purity increases too.
At ternary compound systems with constant CaF2 percent, with increasing
the weight ratio of NaF to A12O3, the product purity increases too.
The best combination of the slag which leads to the best result in this
research is 40% sodium fluoride, 23% alumina, 37% fluorine.
Application of ESCM process in recycling of OFHC copper scraps, results
in a copper with 15-33 ppm oxygen, purity of 99.988%, and electrical
conductivity in excess of 100.1% IACS.

References
[1] Y. Koshiba, T. Masui & N. Iida., "Mitsubishi Materials' High Performance
Oxygen Free Copper And High Performance Alloys", 2nd International
Conference on Processing Materials Properties, TMS, 2000.
[2] R.G. Baligidad, V.V.S. Prasad, G. Balachandran & V. Ramakrishna Rao.,
High Purity Copper Through Electro Slag Crucible Melting, Transactions
of Indian institute of metals,Vol.42, No.3, 1989, pp.339-342.
[3] D. Janicijevic., Modern Plant Produces Oxygen-Free Copper, Metal
Progress, Vol.79, 1961, pp.112-138.
[4] H.A. Blank., "Fabricating OFHC Copper ", Metal Industry, 4 June 1964,
pp.768-770.
[5] J. Crane & E. Shapiro., "High Conductivity High Temperature Copper
Alloy", US Patent No.3976477, 1974.
[6] A.I. Borodin & A.L. Evlevskii, Production of Copper Plates By
Electroslag Mould Casting, Advances in Special ElectroMetallurgy,
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[7] B. Allison., "Copper- The Science and Technology of the Metal, Its Alloys
and
Compounds", Amer. Chem. Soc., Monograph Series, Reinhold
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[8] V.K. Gupta, V.N. Madhav Rao & R.V. Tamhankar., Trans. Indian Inst.
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[9] Anon., Metal Progressing 84 (1963)124.
[10] OFHC Copper, Production and Properties., TR No.125, International
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[11] H. Eckstein., "Working operations and their results for production of
oxygen-free Copper", NEUE HUTTE, Vol.3, No.1, 1958, pp.32-36.
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[12] M. Kameda & A. Yazawa., "Refining of crude copper by Vacuum melting",
Tohoku Daigaku Senko Seiren ken kyusho Tho, Vol.19, No.1, 1963, pp.5768.
[13] D.J. Nesslage, L.S. Yu & M. F. Shaw., "Oxygen-Free Copper Product and
Process", US Patent No.4059437, 1977.
[14] W.J. Yurko & D.K. Peckens., "Method of Producing Oxygen-Free High
Conductivity Copper", US Patent3No.298070, 1965.
[15] A. I. Borodin, B.I. Medovar & B.B. Fedorovskii., "Centrifugal Electroslag
Casting of billets from Copper Scrap", E.O. Paton Welding Institute, Kiev,
Advances in Special Electro- Metallurgy, Vol.1, 1985, pp.23-25.
[16] V.V.S. Prasad, A. Sambasiva Rao, U. Prakash, V. Ramakrishna Rao, P.
Krishna Rao & K.M. Gupt., Alumina Addition to Fluoride Slags for
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Electroslag Crucible Melting, ISIJ International, Vol.38, No.12, 1998,
pp.1387-1398.
[17] V.V.S. Prasad, V. Ramakrishna Rao, U. Prakash, P. Krishna & K.M. Gupt.,
Electro Slag Crucible Melting for Recycling of Low Oxygen High
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pp.1113-1118.

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Materials Characterisation V

407

Author Index
Abud I. ....................................... 77
Ahadi F. K. .............................. 397
Alhoseini S. H.......................... 397
Allison P. G. ............................ 287
Al-Qureshi H. A....................... 165
Alston S. M. ............................. 351
Antorrena G. ............................ 187
Athanasopoulou A. .......... 315, 327
Awietjan S. F. .......................... 263
Ayenk S.................................. 175
Bae G. H. ................................. 213
Barbosa C. ................................. 77
Bestley C. C. N. ....................... 351
Bigdeli Karimi M. ...................... 85
Bobrov M. .................................. 67
Boczkowska A. ........................ 263
Bouzid A.-H............................. 339
Brailovski V. ............................ 339
Brown S. G. R.......................... 351
Bruneton E. .............................. 155
Caminha I. ................................. 77
ern R. ................... 143, 199, 363
Chamis C. C. ............................ 109
Chandler M. Q. ........................ 287
Chicharro J. M. ........................ 275
Christou P. ............................... 131
Chupin S. ................................. 155
Colin J. ..................................... 307
Cummins T. K. ........................ 287
Cvahte P. .................................. 239
Dabek E. .................................... 67
Daniele V. .................................. 55
Darque-Ceretti E. ....................... 15
Dasan B.................................... 251
Dony A. ................................... 307
Dykman M. ................................ 27
Fiala L. ..................................... 143
Freire M. S. .............................. 187

Gabet O...................................... 27
Garland N. ................................. 95
Gonzlez-lvarez J.................. 187
Guagliardo P. ............................... 3
Gueit E. ...................................... 15
Hanaee K. ................................ 397
Herranz G. ............................... 275
Horgnies M. ......................... 15, 27
Hotza D.................................... 165
Huh H. ..................................... 213
Janssen R. ................................ 165
Karako C. ............................... 175
Karpuzova E. ............................. 67
Keide H...................................... 77
Kelekanjeri V. S. K. G. ............ 251
Ketabchi S. .............................. 397
Khan Z. ...................................... 95
Klemm A. J. ................................. 3
Ko V. .................................... 363
Koksal H. O. ............................ 175
Kollaros G. ...................... 315, 327
Kugler G. ................................. 239
Leite E. R. .................................. 41
Lombard S. ................................ 27
Mastromatteo F. ....................... 251
Michael A. ............................... 131
Mihulka J. ................................ 199
Montoro L. A. ............................ 41
Morales A. L. ........................... 275
Moser R. D. ............................. 287
Nascimento J. L. ........................ 77
Nieto A. J. ................................ 275
Northwood D. O. ....................... 85
Ould-Brahim N. ....................... 339
Ouni A. E. ................................ 307

408 Materials Characterisation V


Paimushin V. N........................ 227
Pavlk Z............................ 143, 199
Pavlkov M. .................... 143, 199
Perus I. ..................................... 239
Pintado P. ................................. 275
Plaksin O.................................... 67
Popova G. .................................. 67

Stoilov V. ................................... 85
Stroppa D. G. ............................. 41

Ramirez A. J. ............................. 41
Ros R. ..................................... 187
Rochais D. ............................... 155
Rodrguez G. P......................... 275
Roesler C. R. M. ........................ 77
Rushing T. S. ........................... 287
Ryszkowska J. ................. 377, 387

Vantsyan M. .............................. 67
Vzquez G. .............................. 187
Vejmelkov E. ......................... 143
Vishwanath T........................... 251
Vivet N. ................................... 155
Vborn J. ............................... 363

Saeed A. ..................................... 95
Sakurai H. ................................ 119
Saasiska K. ........................... 387
Samarin S. N. ............................... 3
Silva J. G. P. ............................ 165
Smith R. ..................................... 95
Sondhi S. K. ............................. 251
Song Y. P. ................................ 299

Taglieri G................................... 55
Tercelj M. ................................ 239
Tintillier P. ................................. 15
Turgay T. ................................. 175

Wang H. L. .............................. 299


Waniewski B. ......................... 377
Williams B. A. ......................... 287
Williams J. F. ............................... 3
Willieme P. ................................ 27
Zakirov I. I. .............................. 227
Zakirov I. M............................. 227
umr J. ................................... 199

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